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Sample records for isotropic dft b3lyp

  1. DFT/B3LYP study of tocopherols and chromans antioxidant action energetics

    International Nuclear Information System (INIS)

    Klein, Erik; Lukes, Vladimir; Ilcin, Michal

    2007-01-01

    Gas-phase reaction enthalpies related to the individual steps of three phenolic antioxidants action mechanisms - hydrogen atom transfer (HAT), single-electron transfer-proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET) for four tocopherols and seven chromans - were calculated using DFT/B3LYP method. For α-tocopherol, one of the chromans and phenol, reaction enthalpies in water were computed. In comparison to gas phase, water causes severe changes in the energetics of studied compounds antioxidant action. From the thermodynamic point of view, entering SPLET mechanism represents the most probable process in water

  2. DFT/B3LYP study of tocopherols and chromans antioxidant action energetics

    Energy Technology Data Exchange (ETDEWEB)

    Klein, Erik [Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinskeho 9, SK-812 37 Bratislava (Slovakia)], E-mail: erik.klein@stuba.sk; Lukes, Vladimir; Ilcin, Michal [Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinskeho 9, SK-812 37 Bratislava (Slovakia)

    2007-07-09

    Gas-phase reaction enthalpies related to the individual steps of three phenolic antioxidants action mechanisms - hydrogen atom transfer (HAT), single-electron transfer-proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET) for four tocopherols and seven chromans - were calculated using DFT/B3LYP method. For {alpha}-tocopherol, one of the chromans and phenol, reaction enthalpies in water were computed. In comparison to gas phase, water causes severe changes in the energetics of studied compounds antioxidant action. From the thermodynamic point of view, entering SPLET mechanism represents the most probable process in water.

  3. SCC-TB, DFT/B3LYP, MP2, AM1, PM3 and RHF study of ethylene oxide and propylene oxide structures, VA and VCD spectra

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Frimand, Kenneth

    2002-01-01

    -binding method for equilibrium structures, VA and VCD spectra of ethylene oxide and propylene oxide in the gas-phase. Comparison to conventional methods AM1, PM3, MP2, RHF and DFT/B3LYP is carried out. We report results over a wider range of frequencies than previous work. In particular, we find indications...... that the self-consistent-charge tight-binding method, combined with DFT/B3LYP atomic polar tensors and atomic axial tensors, compares favourably with competing methods tendency to overestimate the location of spectral peaks with respect to frequencies, the latter observation being most pronounced in the higher...... frequency regions. Our findings produce additional support for the self-consistent-charge tight-binding method as a fast computational method for small and larger molecules, however, also that improved parameterisations are needed to reach accuracies of MP2 and DFT/B3LYP. (C) 2002 Elsevier Science B.V. All...

  4. N-propyl nitrate vibrational spectrum analysis using DFT B3LYP quantum-chemical method

    Science.gov (United States)

    Shaikhullina, R. M.; Hrapkovsky, G. M.; Shaikhullina, M. M.

    2018-05-01

    Calculation of a molecular structure, conformation and related vibrational spectra of the n- propyl nitrate C3H7NO3 was carried out by means of density functional theory (DFT) by employing the Gaussian 03 package. The molecular geometries were fully optimized by using the Becker's three-parameter hybrid exchange functional combined with the Lee–Yang–Parr correlation functional (B3LYP) and using the 6-31G(d) basis set. By scanning the dihedral angles around C-O and C-C bonds, five energetically most favorable conformers of n-propyl nitrate - TG, TT, GT, GG and G´G forms were found. Vibrational spectra of the most energetically favorable conformers were calculated. The comparative analysis of calculated and experimental spectra is carried out, the spectral features of the conformational state of n-propyl nitrate and the spectral effects of formation of intramolecular hydrogen bonds are established.

  5. Vibrational investigation on FT-IR and FT-Raman spectra, IR intensity, Raman activity, peak resemblance, ideal estimation, standard deviation of computed frequencies analyses and electronic structure on 3-methyl-1,2-butadiene using HF and DFT (LSDA/B3LYP/B3PW91) calculations.

    Science.gov (United States)

    Ramalingam, S; Jayaprakash, A; Mohan, S; Karabacak, M

    2011-11-01

    FT-IR and FT-Raman (4000-100 cm(-1)) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H). Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  6. FT-IR, FT-Raman, NMR studies and ab initio-HF, DFT-B3LYP vibrational analysis of 4-chloro-2-fluoroaniline.

    Science.gov (United States)

    Arivazhagan, M; Anitha Rexalin, D

    2012-10-01

    The Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectra of 4-chloro-2-fluoroaniline (CFA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of ab initio and density functional theory (DFT) methods. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the Gauge including atomic orbital (GIAO) method. The first order hyperpolarizability (β(0)) of this novel molecular system and related properties (β, α(0) and Δα) of CFA are calculated using B3LYP/6-311++G(d,p) and HF/6-311++G(d,p) methods on the finite-field approach. The calculated results also show that the CFA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The result confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The HOMO-LUMO energies UV-vis spectral analysis and MEP are performed by B3LYP/6-311++G(d,p) approach. A detailed interpretation of the infrared and Raman spectra of CFA is also reported based on total energy distribution (TED). The difference between the observed and scaled wave number values of the most of the fundamentals is very small. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Synthesis, spectroscopic, computational (DFT/B3LYP), AChE inhibition and antioxidant studies of imidazole derivative

    Science.gov (United States)

    Ahmad, Faheem; Alam, Mohammad Jane; Alam, Mahboob; Azaz, Shaista; Parveen, Mehtab; Park, Soonheum; Ahmad, Shabbir

    2018-01-01

    The present study reports the synthesis and evaluation of biological properties of 3a,8a-dihydroxy-8-oxo-1,3,3a,8a-tetrahydroindeno[1,2-d]imidazol-2(1H)-iminium chloride (3). The structure was confirmed by the FTIR, NMR, MS, CHN microanalysis and X-ray crystallographic analysis. Quantum chemical calculations have been performed at B3LYP-D3/6-311++G(d,p) level of theory to study the molecular geometry, IR, (1H and 13C) NMR, UV/Vis spectra and other molecular parameters of the asymmetric unit of crystal of imidazole compound (3). An empirical dispersion correction to hybrid functional (B3LYP-D3) has been incorporated in the present calculations due to presence of non-covalent interaction, Cl⋯H-O, in the present compound. The remarkable agreement has been observed between theoretical data and those measured experimentally. Moreover, the Hirshfeld analysis was carried out to ascertain the secondary interactions and associated 2D fingerprint plots. The synthesized imidazole derivative showed promising antioxidant property and inhibitory activity against acetylcholinesterase (AChE). Molecular docking was also performed in order to explain in silico antioxidant studies and to ascertain the probable binding mode of compound with the amino acid residues of protein.

  8. Ferutinin as a Ca(2+) complexone: lipid bilayers, conductometry, FT-IR, NMR studies and DFT-B3LYP calculations.

    Science.gov (United States)

    Dubis, A; Zamaraeva, M V; Siergiejczyk, L; Charishnikova, O; Shlyonsky, V

    2015-10-07

    Calcium ionophoretic properties of ferutinin were re-evaluated in solvent-containing bilayer lipid membranes. The slopes of conductance-concentration curves suggest that in the presence of a solvent in the membrane the majority of complexes appear to consist of a single terpenoid molecule bound to one Ca ion. By contrast, the stoichiometry of ferutinin-Ca(2+) complexes in acetone determined using the conductometric method was 2 : 1. While the cation-cation selectivity of ferutinin did not change, the cation-anion selectivity slightly decreased in solvent containing membranes. FT-IR and NMR data together with DFT calculations at the B3LYP/6-31G(d) level of theory indicate that in the absence of Ca ions ferutinin molecules are hydrogen-bonded at the phenol hydroxyl groups. The variations of absorption assigned to -OH and -C-O stretching mode suggest that ferutinin interacts strongly with Ca ions via the hydroxyl group of ferutinol and carboxyl oxygen of the complex ether bond. The coordination through the carbonyl group of ferutinin was demonstrated by theoretical calculations. Taken together, ferutinin molecules form H-bonded dimers, while complexation of Ca(2+) by ferutinin ruptures this hydrogen bond due to spatial re-orientation of the ferutinin molecules from parallel to antiparallel alignment.

  9. Conformational, vibrational, NMR and DFT studies of N-methylacetanilide.

    Science.gov (United States)

    Arjunan, V; Santhanam, R; Rani, T; Rosi, H; Mohan, S

    2013-03-01

    A detailed conformational, vibrational, NMR and DFT studies of N-methylacetanilide have been carried out. In DFT, B3LYP method have been used with 6-31G(**), 6-311++G(**) and cc-pVTZ basis sets. The vibrational frequencies were calculated resulting in IR and Raman frequencies together with intensities and Raman depolarisation ratios. The dipole moment derivatives were computed analytically. Owing to the complexity of the molecule, the potential energy distributions of the vibrational modes of the compound are also calculated. Isoelectronic molecular electrostatic potential surface (MEP) and electron density surface were examined. (1)H and (13)C NMR isotropic chemical shifts were calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound were also determined from TD-DFT method. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. DFT:B3LYP/3-21G theoretical insights on the confocal Raman experimental observations in skin dermis of healthy young, healthy elderly, and diabetic elderly women

    Science.gov (United States)

    Téllez Soto, Claudio Alberto; Pereira, Liliane; dos Santos, Laurita; Rajasekaran, Ramu; Fávero, Priscila; Martin, Airton Abrahão

    2016-12-01

    In the confocal Raman spectra of skin dermis, the band area in the spectral region of proline and hydroxyproline varies according to the age and health condition of the volunteers, classified as healthy young women, healthy elderly women, and diabetic elderly women. Another observation refers to the intensity variation and negative Raman shift of the amide I band. To understand these effects, we adopted a model system using the DFT/B3LYP:3-21G procedure, considering the amino acid chain formed by glycine, hydroxyproline, proline, and alanine, which interacts with two and six water molecules. Through these systems, polarizability variations were analyzed to correlate its values with the observed Raman intensities of the three groups of volunteers and to assign the vibrational spectra of the skin dermis. As a way to correlate other experimental trends, we propose a model of chemical reaction of water interchange between the bonding amino acids, in which water molecules are attached with glucose by hydrogen bonds. The theoretical results are in accordance with the observed experimental trends.

  11. Evaluation of DFT methods for computing the interaction energies of homomolecular and heteromolecular dimers of monosubstituted benzene

    Science.gov (United States)

    Godfrey-Kittle, Andrew; Cafiero, Mauricio

    We present density functional theory (DFT) interaction energies for the sandwich and T-shaped conformers of substituted benzene dimers. The DFT functionals studied include TPSS, HCTH407, B3LYP, and X3LYP. We also include Hartree-Fock (HF) and second-order Møller-Plesset perturbation theory calculations (MP2), as well as calculations using a new functional, P3LYP, which includes PBE and HF exchange and LYP correlation. Although DFT methods do not explicitly account for the dispersion interactions important in the benzene-dimer interactions, we find that our new method, P3LYP, as well as HCTH407 and TPSS, match MP2 and CCSD(T) calculations much better than the hybrid methods B3LYP and X3LYP methods do.

  12. Structural, Spectroscopic (FT-IR, Raman and NMR, Non-linear Optical (NLO, HOMO-LUMO and Theoretical (DFT/CAM-B3LYP Analyses of N-Benzyloxycarbonyloxy-5-Norbornene-2,3-Dicarboximide Molecule

    Directory of Open Access Journals (Sweden)

    Nuri ÖZTÜRK

    2018-02-01

    Full Text Available The experimental spectroscopic investigation of N-benzyloxycarbonyloxy-5-norbornene-2,3-dicarboximide (C17H15NO5 molecule has been done using 1H and 13C NMR chemical shifts, FT-IR and Raman spectroscopies. Conformational forms have been determined depending on orientation of N-benzyloxycarbonyloxy and 5-norbornene-2,3-dicarboximide (NDI groups of the title compound. The structural geometric optimizations, vibrational wavenumbers, NMR chemical shifts (in vacuum and chloroform and HOMO-LUMO analyses for all conformers of the title molecule have been done with DFT/CAM-B3LYP method at the 6-311++G(d,p basis set. Additionally, based on the calculated HOMO and LUMO energy values, some molecular properties such as ionization potential (I, electron affinity (A, electronegativity (χ, chemical hardness (h, chemical softness (z, chemical potential (μ and electrophilicity index (w parameters are determined for all conformers. The non-linear optical (NLO properties have been studied for the title molecule. We can say that the experimental spectral data are in accordance with calculated values.

  13. DFT and TD-DFT computation of charge transfer complex between o-phenylenediamine and 3,5-dinitrosalicylic acid

    International Nuclear Information System (INIS)

    Afroz, Ziya; Zulkarnain,; Ahmad, Afaq; Alam, Mohammad Jane; Faizan, Mohd; Ahmad, Shabbir

    2016-01-01

    DFT and TD-DFT studies of o-phenylenediamine (PDA), 3,5-dinitrosalicylic acid (DNSA) and their charge transfer complex have been carried out at B3LYP/6-311G(d,p) level of theory. Molecular geometry and various other molecular properties like natural atomic charges, ionization potential, electron affinity, band gap, natural bond orbital (NBO) and frontier molecular analysis have been presented at same level of theory. Frontier molecular orbital and natural bond orbital analysis show the charge delocalization from PDA to DNSA.

  14. Structural, electronic and vibrational properties of GexCy (x+y=2-5) nanoclusters: A B3LYP-DFT study

    Science.gov (United States)

    Goswami, Sohini; Saha, Sushmita; Yadav, R. K.

    2015-11-01

    An ab-initio study of the stability, structural and electronic properties has been made for 84 germanium carbide nanoclusters, GexCy (x+y=2-5). The configuration possessing the maximum value of final binding energy (FBE), among the various configurations corresponding to a fixed x+y=n value, is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize fully the geometries of the nanoclusters. The binding energies (BE), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps have been obtained for all the clusters and the bond lengths have been reported for the most stable clusters. We have considered the zero point energy (ZPE) corrections. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have also been investigated for the most stable structures. The configurations containing the carbon atoms in majority are seen to be the most stable structures. The strong C-C bond has important role in stabilizing the clusters. For the clusters containing one germanium atom and all the other as carbon atoms, the BE increases monotonically with the number of the carbon atoms. The HOMO-LUMO gap, IPs and EAs fluctuates with increase in the number of atoms. The nanoclusters containing even number of carbon atoms have large HOMO-LUMO gaps and IPs, whereas the nanoclusters containing even number of carbon atoms have small EAs. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA). The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the

  15. Evaluation of B3LYP, X3LYP, and M06-Class Density Functionals for Predicting the Binding Energies of Neutral, Protonated, and Deprotonated Water Clusters.

    Science.gov (United States)

    Bryantsev, Vyacheslav S; Diallo, Mamadou S; van Duin, Adri C T; Goddard, William A

    2009-04-14

    In this paper we assess the accuracy of the B3LYP, X3LYP, and newly developed M06-L, M06-2X, and M06 functionals to predict the binding energies of neutral and charged water clusters including (H2O)n, n = 2-8, 20), H3O(+)(H2O)n, n = 1-6, and OH(-)(H2O)n, n = 1-6. We also compare the predicted energies of two ion hydration and neutralization reactions on the basis of the calculated binding energies. In all cases, we use as benchmarks calculated binding energies of water clusters extrapolated to the complete basis set limit of the second-order Møller-Plesset perturbation theory with the effects of higher order correlation estimated at the coupled-cluster theory with single, double, and perturbative triple excitations in the aug-cc-pVDZ basis set. We rank the accuracy of the functionals on the basis of the mean unsigned error (MUE) between calculated benchmark and density functional theory energies. The corresponding MUE (kcal/mol) for each functional is listed in parentheses. We find that M06-L (0.73) and M06 (0.84) give the most accurate binding energies using very extended basis sets such as aug-cc-pV5Z. For more affordable basis sets, the best methods for predicting the binding energies of water clusters are M06-L/aug-cc-pVTZ (1.24), B3LYP/6-311++G(2d,2p) (1.29), and M06/aug-cc-PVTZ (1.33). M06-L/aug-cc-pVTZ also gives more accurate energies for the neutralization reactions (1.38), whereas B3LYP/6-311++G(2d,2p) gives more accurate energies for the ion hydration reactions (1.69).

  16. Halogen effect on structure and 13C NMR chemical shift of 3,6-disubstituted-N-alkyl carbazoles

    DEFF Research Database (Denmark)

    Radula-Janik, Klaudia; Kupka, Teobald; Ejsmont, Krzysztof

    2013-01-01

    Structures of selected 3,6-dihalogeno-N-alkyl carbazole derivatives were calculated at the B3LYP/6-311++G(3df,2pd) level of theory and their 13C NMR isotropic nuclear shieldings were predicted using density functional theory (DFT). The model compounds contained 9H-, N-methyl and N-ethyl derivatives...

  17. Evaluation of B3LYP, X3LYP, and M06-class density functionals for predicting the binding energies of neutral, protonated, and deprotonated water clusters

    OpenAIRE

    Bryantsev, Vyacheslav S.; Diallo, Mamadou S.; van Duin, Adri C. T.; Goddard, William A., III

    2009-01-01

    In this paper we assess the accuracy of the B3LYP, X3LYP, and newly developed M06-L, M06-2X, and M06 functionals to predict the binding energies of neutral and charged water clusters including (H_2O)_n, n = 2−8, 20), H_3O+(H_2O_)n, n = 1−6, and OH−(H_2O)_n, n = 1−6. We also compare the predicted energies of two ion hydration and neutralization reactions on the basis of the calculated binding energies. In all cases, we use as benchmarks calculated binding energies of water clusters extrapolate...

  18. Structural, electronic and vibrational properties of small GaxNy (x+y = 2-5) nanoclusters: a B3LYP-DFT study

    International Nuclear Information System (INIS)

    Yadav, P S; Yadav, R K; Agrawal, B K

    2007-01-01

    An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, Ga x N y (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the

  19. Machine Learning Methods to Predict Density Functional Theory B3LYP Energies of HOMO and LUMO Orbitals.

    Science.gov (United States)

    Pereira, Florbela; Xiao, Kaixia; Latino, Diogo A R S; Wu, Chengcheng; Zhang, Qingyou; Aires-de-Sousa, Joao

    2017-01-23

    Machine learning algorithms were explored for the fast estimation of HOMO and LUMO orbital energies calculated by DFT B3LYP, on the basis of molecular descriptors exclusively based on connectivity. The whole project involved the retrieval and generation of molecular structures, quantum chemical calculations for a database with >111 000 structures, development of new molecular descriptors, and training/validation of machine learning models. Several machine learning algorithms were screened, and an applicability domain was defined based on Euclidean distances to the training set. Random forest models predicted an external test set of 9989 compounds achieving mean absolute error (MAE) up to 0.15 and 0.16 eV for the HOMO and LUMO orbitals, respectively. The impact of the quantum chemical calculation protocol was assessed with a subset of compounds. Inclusion of the orbital energy calculated by PM7 as an additional descriptor significantly improved the quality of estimations (reducing the MAE in >30%).

  20. Trans-dinitroglycoluril isomers-A DFT treatment

    Directory of Open Access Journals (Sweden)

    Lemi Türker

    2017-02-01

    Full Text Available Isomers of trans-1,4-Dinitroglycoluril (trans-DINGU and their 1,3-tautomers are considered within the constraints of B3LYP/6-31++G (d,p and B3LYP/CC-PVTZ levels of DFT calculations. Additionally, the interactions of these isomers and proton in vacuum are investigated. The data have revealed that two of the three isomers undergo CH bond cleavage as the result of interaction with proton in vacuum. The total energies, some structural properties, the calculated IR and UV spectra are discussed.

  1. Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine

    Science.gov (United States)

    Srivastava, Santosh K.; Singh, Vipin B.

    2013-11-01

    Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.

  2. Quantum-chemical ab initio and B3LYP investigation of tricyanides and triisocyanides of Al, Ga, In

    International Nuclear Information System (INIS)

    Timoshkin, A.Yu.; Shefer, G.F.

    2000-01-01

    Ab initio and density functional B3LYP methods are used to obtain structural parameters, standard entropies and vibrational spectra of cyanides and isocyanides of trivalent Al, Ga, In for the first time. It is pointed out that for In cyanide form is more stable. There is divergence in data obtained in the framework of self-consistent field and by B3LYP methods what indicates importance of estimation of energy of electronic correlation and in the same time comparison of basic sets DZP and LANL2DZP demonstrates insufficiency of basic sets with effective potentials of skeleton for description molecular tricyanides of elements of the 3a group [ru

  3. (E-2-Acetyl-4-[(3-methylphenyldiazenyl]phenol: an X-ray and DFT study

    Directory of Open Access Journals (Sweden)

    Orhan Büyükgüngör

    2010-03-01

    Full Text Available The title compound, C15H14N2O2, an azo dye, displays a trans configuration with respect to the N=N bridge. The dihedral angle between the aromatic rings is 0.18 (14°. There is a strong intramolecular O—H...O hydrogen bond. Geometrical parameters, determined using X-ray diffraction techniques, are compared with those calculated by density functional theory (DFT, using hybrid exchange–correlation functional, B3LYP and semi-empirical (PM3 methods.

  4. Computing sextic centrifugal distortion constants by DFT: A benchmark analysis on halogenated compounds

    Science.gov (United States)

    Pietropolli Charmet, Andrea; Stoppa, Paolo; Tasinato, Nicola; Giorgianni, Santi

    2017-05-01

    This work presents a benchmark study on the calculation of the sextic centrifugal distortion constants employing cubic force fields computed by means of density functional theory (DFT). For a set of semi-rigid halogenated organic compounds several functionals (B2PLYP, B3LYP, B3PW91, M06, M06-2X, O3LYP, X3LYP, ωB97XD, CAM-B3LYP, LC-ωPBE, PBE0, B97-1 and B97-D) were used for computing the sextic centrifugal distortion constants. The effects related to the size of basis sets and the performances of hybrid approaches, where the harmonic data obtained at higher level of electronic correlation are coupled with cubic force constants yielded by DFT functionals, are presented and discussed. The predicted values were compared to both the available data published in the literature and those obtained by calculations carried out at increasing level of electronic correlation: Hartree-Fock Self Consistent Field (HF-SCF), second order Møller-Plesset perturbation theory (MP2), and coupled-cluster single and double (CCSD) level of theory. Different hybrid approaches, having the cubic force field computed at DFT level of theory coupled to harmonic data computed at increasing level of electronic correlation (up to CCSD level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T)) were considered. The obtained results demonstrate that they can represent reliable and computationally affordable methods to predict sextic centrifugal terms with an accuracy almost comparable to that yielded by the more expensive anharmonic force fields fully computed at MP2 and CCSD levels of theory. In view of their reduced computational cost, these hybrid approaches pave the route to the study of more complex systems.

  5. Synthesis, electronic structure investigation of 3-pentyl-2,6-di(furan-2-yl)piperidin-4-one by FT-IR, FT-Raman and UV-Visible spectral studies and ab initio/DFT calculations.

    Science.gov (United States)

    Arockia Doss, M; Savithiri, S; Rajarajan, G; Thanikachalam, V; Anbuselvan, C

    2015-12-05

    FT-IR and FT-Raman spectra of 3-pentyl-2,6-di(furan-2-yl) piperidin-4-one (3-PFPO) were recorded in the solid phase. The structural and spectroscopic analyses of 3-PFPO were made by using B3LYP/HF level with 6-311++G(d, p) basis set. The fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3-PFPO with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The electronic properties such as excitation energies, oscillator strength, wavelengths and HOMO-LUMO energies were obtained by time-dependent DFT (TD-DFT) approach. The polarizability and first order hyperpolarizability of the title molecule were calculated and interpreted. The hyperconjugative interaction energy (E((2))) and electron densities of donor (i) and acceptor (j) bonds were calculated using NBO analysis. In addition, MEP and atomic charges of carbon, nitrogen, oxygen and hydrogen were calculated using B3LYP/6-311++G(d, p) level theory. Moreover, thermodynamic properties (heat capacities, entropy and enthalpy) of the title compound at different temperatures were calculated in gas phase. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

    International Nuclear Information System (INIS)

    Berardo, Enrico; Hu, Han-Shi; Van Dam, Hubertus J. J.; Shevlin, Stephen A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.

    2014-01-01

    We have investigated the description of excited state relaxation in naked and hydrated TiO 2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO 2 nanoparticles is predicted to be associated with a large Stokes' shift

  7. Synthesis, Crystal Structure, and DFT Calculations of 1,3-Diisobutyl Thiourea

    Directory of Open Access Journals (Sweden)

    Ataf A. Altaf

    2015-01-01

    Full Text Available 1,3-Diisobutyl thiourea was synthesized and characterized by single crystal X-ray diffraction. It gives a monoclinic (α = γ = 90 and β  ≠ 90 structure with the space group P21/c. The unit cell dimensions are a = 11.5131 (4 Å, b = 9.2355 (3 Å, c = 11.3093 (5 Å, α = 90°, β = 99.569° (2, γ = 90°, V = 1185.78 (8 Å3, and Z = 4. The crystal packing is stabilized by intermolecular (N–H⋯S hydrogen bonding in the molecules. The optimized geometry and Mullikan's charges of the said molecule calculated with the help of DFT using B3LYP-6-311G model support the crystal structure.

  8. Structural, electronic and vibrational properties of small Ga{sub x}N{sub y} (x+y = 2-5) nanoclusters: a B3LYP-DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, P S; Yadav, R K; Agrawal, B K [Physics Department, Allahabad University, Allahabad-211002 (India)

    2007-02-21

    An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, Ga{sub x}N{sub y} (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster

  9. FT-IR and Raman vibrational analysis, B3LYP and M06-2X simulations of 4-bromomethyl-6-tert-butyl-2H-chromen-2-one

    Science.gov (United States)

    Sert, Yusuf; Puttaraju, K. B.; Keskinoğlu, Sema; Shivashankar, K.; Ucun, Fatih

    2015-01-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized bacteriostatic and anti-tumor molecule namely, 4-bromomethyl-6-tert-butyl-2H-chromen-2-one have been investigated. The experimental FT-IR (4000-400 cm-1) and Raman spectra (4000-100 cm-1) of the compound in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters have been calculated using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: highly parametrized, empirical exchange correlation function) with 6-311++G(d, p) basis set by Gaussian 03 software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated using the same theoretical calculations.

  10. Appropriate description of intermolecular interactions in the methane hydrates: an assessment of DFT methods.

    Science.gov (United States)

    Liu, Yuan; Zhao, Jijun; Li, Fengyu; Chen, Zhongfang

    2013-01-15

    Accurate description of hydrogen-bonding energies between water molecules and van der Waals interactions between guest molecules and host water cages is crucial for study of methane hydrates (MHs). Using high-level ab initio MP2 and CCSD(T) results as the reference, we carefully assessed the performance of a variety of exchange-correlation functionals and various basis sets in describing the noncovalent interactions in MH. The functionals under investigation include the conventional GGA, meta-GGA, and hybrid functionals (PBE, PW91, TPSS, TPSSh, B3LYP, and X3LYP), long-range corrected functionals (ωB97X, ωB97, LC-ωPBE, CAM-B3LYP, and LC-TPSS), the newly developed Minnesota class functionals (M06-L, M06-HF, M06, and M06-2X), and the dispersion-corrected density functional theory (DFT) (DFT-D) methods (B97-D, ωB97X-D, PBE-TS, PBE-Grimme, and PW91-OBS). We found that the conventional functionals are not suitable for MH, notably, the widely used B3LYP functional even predicts repulsive interaction between CH(4) and (H(2)O)(6) cluster. M06-2X is the best among the M06-Class functionals. The ωB97X-D outperforms the other DFT-D methods and is recommended for accurate first-principles calculations of MH. B97-D is also acceptable as a compromise of computational cost and precision. Considering both accuracy and efficiency, B97-D, ωB97X-D, and M06-2X functional with 6-311++G(2d,2p) basis set without basis set superposition error (BSSE) correction are recommended. Though a fairly large basis set (e.g., aug-cc-pVTZ) and BSSE correction are necessary for a reliable MP2 calculation, DFT methods are less sensitive to the basis set and BSSE correction if the basis set is sufficient (e.g., 6-311++G(2d,2p)). These assessments provide useful guidance for choosing appropriate methodology of first-principles simulation of MH and related systems. © 2012 Wiley Periodicals, Inc. Copyright © 2012 Wiley Periodicals, Inc.

  11. Theoretical (in B3LYP/6-3111++G** level), spectroscopic (FT-IR, FT-Raman) and thermogravimetric studies of gentisic acid and sodium, copper(II) and cadmium(II) gentisates.

    Science.gov (United States)

    Regulska, E; Kalinowska, M; Wojtulewski, S; Korczak, A; Sienkiewicz-Gromiuk, J; Rzączyńska, Z; Swisłocka, R; Lewandowski, W

    2014-11-11

    The DFT calculations (B3LYP method with 6-311++G(d,p) mixed with LanL2DZ for transition metals basis sets) for different conformers of 2,5-dihydroxybenzoic acid (gentisic acid), sodium 2,5-dihydroxybenzoate (gentisate) and copper(II) and cadmium(II) gentisates were done. The proposed hydrated structures of transition metal complexes were based on the results of experimental findings. The theoretical geometrical parameters and atomic charge distribution were discussed. Moreover Na, Cu(II) and Cd(II) gentisates were synthesized and the composition of obtained compounds was revealed by means of elemental and thermogravimetric analyses. The FT-IR and FT-Raman spectra of gentisic acid and gentisates were registered and the effect of metals on the electronic charge distribution of ligand was discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Pyrone-based Cu(II) complexes, their characterization, DFT based ...

    Indian Academy of Sciences (India)

    ... of P. G. Studies and. Research in Chemistry and Pharmacy, R. D. University, Jabalpur 482 001, India ... fascination.2,3 Such type of metal complexes are quite interesting due to .... in the ground state were optimized by the DFT method using B3LYP ..... Vogel A I 1996 In A Text Book of Qualitative Inorganic. Analysis (7th ...

  13. Structural, vibrational and nuclear magnetic resonance investigations of 4-bromoisoquinoline by experimental and theoretical DFT methods.

    Science.gov (United States)

    Arjunan, V; Thillai Govindaraja, S; Jayapraksh, A; Mohan, S

    2013-04-15

    Quantum chemical calculations of energy, structural parameters and vibrational wavenumbers of 4-bromoisoquinoline (4BIQ) were carried out by using B3LYP method using 6-311++G(**), cc-pVTZ and LANL2DZ basis sets. The optimised geometrical parameters obtained by DFT calculations are in good agreement with electron diffraction data. Interpretations of the experimental FTIR and FT-Raman spectra have been reported with the aid of the theoretical wavenumbers. The differences between the observed and scaled wavenumber values of most of the fundamentals are very small. The thermodynamic parameters have also been computed. Electronic properties of the molecule were discussed through the molecular electrostatic potential surface, HOMO-LUMO energy gap and NBO analysis. To provide precise assignments of (1)H and (13)CNMR spectra, isotropic shielding and chemical shifts were calculated with the Gauge-Invariant Atomic Orbital (GIAO) method. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. N-2-Aryl-1,2,3-Triazoles: A novel class of blue–green emitting fluorophores-synthesis, photophysical properties study and dft computations

    Energy Technology Data Exchange (ETDEWEB)

    Padalkar, Vikas S.; Chemate, Santosh B.; Lanke, Sandip K.; Sekar, Nagaiyan, E-mail: n.sekar@ictmumbai.edu.in

    2015-12-15

    Three novel 2-{2-[4-(N,N-diethylamino)–2–hydroxyphenyl]–1H–benzo[d]imidazol–6–yl} –2H–naphtho [1,2-d] [1,2,3] fluorescent triazole derivatives were synthesized from 2-(5-amino-1H-benzimidazol-2-yl)-5-(N,N-diethylamino)phenol and amino substituted naphthylsulphonic acids. The absorption, emission, quantum yields and dipole moments of these compounds were evaluated in methanol, acetonitrile, N,N-dimethylformamide and dimethylsulfoxide. The compounds 8a and 8c absorb in the near visible region, while compound 8b shows two absorption peaks, short wavelength peak is in the near visible region and long wavelength absorption in the visible region. Compounds are fluorescent in solution and emit in blue and green region. The photophysical properties of the 8a–8c were compared with structural analogs reported till date. The experimental absorption and emission properties were compared with the theoretical data obtained by DFT and TD-DFT computations with TD–B3LYP and CAM–B3LYP functional with 6–31G (d) and 6–311G (d) basis sets. Theoretical results obtained by TD-B3LYP functional are well in line with the experimental results. The compounds are thermally stable up to 300 °C. New compounds were characterized by spectral techniques. - Highlights: • First unique study of blue-emitting ESIPT triazoles. • Improved photophysical properties compared to similar analogues. • Experimental and TDDFT data on photophysical properties. • Dipole moments from solvatochromic data.

  15. Ab Initio and DFT Potential Energy Surfaces for Cyanuric Chloride Reactions

    National Research Council Canada - National Science Library

    Pai, Sharmila

    1998-01-01

    ... on the potential energy surface were calculated using the 6-31G and 6-311 +Gbasis sets. DFT(B3LYP) geometry optimizations and zero-point corrections for critical points on the potential energy surface were calculated with the 6-31G, 6-311...

  16. Estimation of optical rotation of γ-alkylidenebutenolide, cyclopropylamine, cyclopropyl-methanol and cyclopropenone based compounds by a Density Functional Theory (DFT) approach.

    Science.gov (United States)

    Shahzadi, Iram; Shaukat, Aqsa; Zara, Zeenat; Irfan, Muhammad; Eliasson, Bertil; Ayub, Khurshid; Iqbal, Javed

    2017-10-01

    Computing the optical rotation of organic molecules can be a real challenge, and various theoretical approaches have been developed in this regard. A benchmark study of optical rotation of various classes of compounds was carried out by Density Functional Theory (DFT) methods. The aim of the present research study was to find out the best-suited functional and basis set to estimate the optical rotations of selected compounds with respect to experimental literature values. Six DFT functional LSDA, BVP86, CAM-B3LYP, B3PW91, and PBE were applied on 22 different compounds. Furthermore, six different basis sets, i.e., 3-21G, 6-31G, aug-cc-pVDZ, aug-cc-pVTZ, DGDZVP, and DGDZVP2 were also applied with the best-suited functional B3LYP. After rigorous effort, it can be safely said that the best combination of functional and basis set is B3LYP/aug-cc-pVTZ for the estimation of optical rotation for selected compounds. © 2017 Wiley Periodicals, Inc.

  17. Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Webster, R., E-mail: ross.webster07@imperial.ac.uk; Harrison, N. M. [Thomas Young Centre, Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ (United Kingdom); Bernasconi, L. [Rutherford Appleton Laboratory, STFC, Harwell Oxford, Didcot OX11 0QX (United Kingdom)

    2015-06-07

    We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.

  18. DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state

    Science.gov (United States)

    Hanuza, J.; Godlewska, P.; Lisiecki, R.; Ryba-Romanowski, W.; Kadłubański, P.; Lorenc, J.; Łukowiak, A.; Macalik, L.; Gerasymchuk, Yu.; Legendziewicz, J.

    2018-05-01

    The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln = Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.

  19. An improved synthesis, spectroscopic (FT-IR, NMR) study and DFT computational analysis (IR, NMR, UV-Vis, MEP diagrams, NBO, NLO, FMO) of the 1,5-methanoazocino[4,3-b]indole core structure

    Science.gov (United States)

    Uludağ, Nesimi; Serdaroğlu, Goncagül

    2018-03-01

    This study examines the synthesis of azocino[4,3-b]indole structure, which constitutes the tetracyclic framework of uleine, dasycarpidoneand tubifolidineas well as ABDE substructure of the strychnosalkaloid family. It has been synthesized by Fischer indolization of 2 and through the cylization of 4 by 2,3-dichlor-5-6-dicyanobenzoquinone (DDQ). 1H and 1C NMR chemical shifts have been predicted with GIAO approach and the calculated chemical shifts show very good agreement with observed shifts. FT-IR spectroscopy is important for the analysis of functional groups of synthesized compounds and we also supported FT-IR vibrational analysis with computational IR analysis. The vibrational spectral analysis was performed at B3LYP level of the theory in both the gas and the water phases and it was compared with the observed IR values for the important functional groups. The DFT calculations have been conducted to determine the most stable structure of the 1,2,3,4,5,6,7-Hexahydro-1,5-methanoazocino [4,3-b] indole (5). The Frontier Molecular Orbital Analysis, quantum chemical parameters, physicochemical properties have been predicted by using the same theory of level in both gas phase and the water phase, at 631 + g** and 6311++g** basis sets. TD- DFT calculations have been performed to predict the UV- Vis spectral analysis for this synthesized molecule. The Natural Bond Orbital (NBO) analysis have been performed at B3LYP level of theory to elucidate the intra-molecular interactions such as electron delocalization and conjugative interactions. NLO calculations were conducted to obtain the electric dipole moment and polarizability of the title compound.

  20. Charge transfer complex between 2,3-diaminopyridine with chloranilic acid. Synthesis, characterization and DFT, TD-DFT computational studies

    Science.gov (United States)

    Al-Ahmary, Khairia M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

    2018-05-01

    New charge transfer complex (CTC) between the electron donor 2,3-diaminopyridine (DAP) with the electron acceptor chloranilic (CLA) acid has been synthesized and characterized experimentally and theoretically using a variety of physicochemical techniques. The experimental work included the use of elemental analysis, UV-vis, IR and 1H NMR studies to characterize the complex. Electronic spectra have been carried out in different hydrogen bonded solvents, methanol (MeOH), acetonitrile (AN) and 1:1 mixture from AN-MeOH. The molecular composition of the complex was identified to be 1:1 from Jobs and molar ratio methods. The stability constant was determined using minimum-maximum absorbances method where it recorded high values confirming the high stability of the formed complex. The solid complex was prepared and characterized by elemental analysis that confirmed its formation in 1:1 stoichiometric ratio. Both IR and NMR studies asserted the existence of proton and charge transfers in the formed complex. For supporting the experimental results, DFT computations were carried out using B3LYP/6-31G(d,p) method to compute the optimized structures of the reactants and complex, their geometrical parameters, reactivity parameters, molecular electrostatic potential map and frontier molecular orbitals. The analysis of DFT results strongly confirmed the high stability of the formed complex based on existing charge transfer beside proton transfer hydrogen bonding concordant with experimental results. The origin of electronic spectra was analyzed using TD-DFT method where the observed λmax are strongly consisted with the computed ones. TD-DFT showed the contributed states for various electronic transitions.

  1. Spectroscopic Investigations and DFT Calculations on 3-(Diacetylamino-2-ethyl-3H-quinazolin-4-one

    Directory of Open Access Journals (Sweden)

    Yusuf Sert

    2016-01-01

    Full Text Available The theoretical and experimental vibrational frequencies of 3-(diacetylamino-2-ethyl-3H-quinazolin-4-one (2 were investigated. The experimental Laser-Raman spectrum (4000–100 cm−1 and FT-IR spectrum (4000–400 cm−1 of the newly synthesized compound were recorded in the solid phase. Both the theoretical vibrational frequencies and the optimized geometric parameters such as bond lengths and bond angles have for the first time been calculated using density functional theory (DFT/B3LYP and DFT/M06-2X quantum chemical methods with the 6-311++G(d,p basis set using Gaussian 03 software. The vibrational frequencies were assigned with the help of potential energy distribution (PED analysis using VEDA 4 software. The calculated vibrational frequencies and the optimized geometric parameters were found to be in good agreement with the corresponding reported experimental data. Also, the energies of the lowest unoccupied molecular orbital (LUMO, highest occupied molecular orbital (HOMO, and other related molecular energies for 3-(diacetylamino-2-ethyl-3H-quinazolin-4-one (2 have been investigated using the same computational methods.

  2. Density-functional approaches to noncovalent interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals.

    Science.gov (United States)

    Burns, Lori A; Vázquez-Mayagoitia, Alvaro; Sumpter, Bobby G; Sherrill, C David

    2011-02-28

    A systematic study of techniques for treating noncovalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength compiled for molecular complexes of diverse size and nature. In particular, the efficacy of functionals deliberately crafted to encompass long-range forces, a posteriori DFT+dispersion corrections (DFT-D2 and DFT-D3), and exchange-hole dipole moment (XDM) theory is assessed against a large collection (469 energy points) of reference interaction energies at the CCSD(T) level of theory extrapolated to the estimated complete basis set limit. The established S22 [revised in J. Chem. Phys. 132, 144104 (2010)] and JSCH test sets of minimum-energy structures, as well as collections of dispersion-bound (NBC10) and hydrogen-bonded (HBC6) dissociation curves and a pairwise decomposition of a protein-ligand reaction site (HSG), comprise the chemical systems for this work. From evaluations of accuracy, consistency, and efficiency for PBE-D, BP86-D, B97-D, PBE0-D, B3LYP-D, B970-D, M05-2X, M06-2X, ωB97X-D, B2PLYP-D, XYG3, and B3LYP-XDM methodologies, it is concluded that distinct, often contrasting, groups of these elicit the best performance within the accessible double-ζ or robust triple-ζ basis set regimes and among hydrogen-bonded or dispersion-dominated complexes. For overall results, M05-2X, B97-D3, and B970-D2 yield superior values in conjunction with aug-cc-pVDZ, for a mean absolute deviation of 0.41 - 0.49 kcal/mol, and B3LYP-D3, B97-D3, ωB97X-D, and B2PLYP-D3 dominate with aug-cc-pVTZ, affording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 - 0.38 kcal/mol.

  3. 3-Iodobenzaldehyde: XRD, FT-IR, Raman and DFT studies.

    Science.gov (United States)

    Kumar, Chandraju Sadolalu Chidan; Parlak, Cemal; Tursun, Mahir; Fun, Hoong-Kun; Rhyman, Lydia; Ramasami, Ponnadurai; Alswaidan, Ibrahim A; Keşan, Gürkan; Chandraju, Siddegowda; Quah, Ching Kheng

    2015-06-15

    The structure of 3-iodobenzaldehyde (3IB) was characterized by FT-IR, Raman and single-crystal X-ray diffraction techniques. The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 3IB were examined using density functional theory (DFT) method, with the Becke-3-Lee-Yang-Parr (B3LYP) functional and the 6-311+G(3df,p) basis set for all atoms except for iodine. The LANL2DZ effective core basis set was used for iodine. Potential energy distribution (PED) analysis of normal modes was performed to identify characteristic frequencies. 3IB crystallizes in monoclinic space group P21/c with the O-trans form. There is a good agreement between the theoretically predicted structural parameters, and vibrational frequencies and those obtained experimentally. In order to understand halogen effect, 3-halogenobenzaldehyde [XC6H4CHO; X=F, Cl and Br] was also studied theoretically. The free energy difference between the isomers is small but the rotational barrier is about 8kcal/mol. An atypical behavior of fluorine affecting conformational preference is observed. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. A Mechanistic Study of Hydroboration of 1-Octene with 1,3,2 ...

    African Journals Online (AJOL)

    dithiaborinane in their ground states have been studied using density functional theory (DFT) at the B3LYP/3-21+G and B3LYP/6-31+G(d) levels. Hydroboration and disproportionation transition states have been determined and activation energies ...

  5. Electron Affinity of trans-2-C4F8 from Electron Attachment-Detachment Kinetics

    Science.gov (United States)

    2009-09-04

    0.989, for DFT results. b Hartree units; G3(MP2) formalism and B3LYP/6-31+G(3df)// B3LYP/6-31+G(3df) + ZPE for DFT results. c Difference between the...units; G3(MP2) formalism and B3LYP/6-31+G(3df)// B3LYP/6-31+G(3df) + ZPE for DFT results. c Difference between the anion total energy at 0 K and that

  6. An extended hybrid density functional (X3LYP) with improved descriptions of nonbond interactions and thermodynamic properties of molecular systems

    Science.gov (United States)

    Xu, Xin; Zhang, Qingsong; Muller, Richard P.; Goddard, William A.

    2005-01-01

    We derive here the form for the exact exchange energy density for a density that decays with Gaussian-type behavior at long range. This functional is intermediate between the B88 and the PW91 exchange functionals. Using this modified functional to match the form expected for Gaussian densities, we propose the X3LYP extended functional. We find that X3LYP significantly outperforms Becke three parameter Lee-Yang-Parr (B3LYP) for describing van der Waals and hydrogen bond interactions, while performing slightly better than B3LYP for predicting heats of formation, ionization potentials, electron affinities, proton affinities, and total atomic energies as validated with the extended G2 set of atoms and molecules. Thus X3LYP greatly enlarges the field of applications for density functional theory. In particular the success of X3LYP in describing the water dimer (with Re and De within the error bars of the most accurate determinations) makes it an excellent candidate for predicting accurate ligand-protein and ligand-DNA interactions.

  7. Vibrational spectroscopy (FT-IR and Laser-Raman) investigation, and computational (M06-2X and B3LYP) analysis on the structure of 4-(3-fluorophenyl)-1-(propan-2-ylidene)-thiosemicarbazone.

    Science.gov (United States)

    Sert, Yusuf; Miroslaw, Barbara; Çırak, Çağrı; Doğan, Hatice; Szulczyk, Daniel; Struga, Marta

    2014-07-15

    In this study, the experimental and theoretical vibrational spectral analysis of 4-(3-fluorophenyl)-1-(propan-2-ylidene)-thiosemicarbazone have been carried out. The experimental FT-IR (4000-400 cm(-1)) and Laser-Raman spectra (4000-100 cm(-1)) have been recorded for the solid state samples. The theoretical vibrational frequencies and the optimized geometric parameters (bond lengths and angles) have been calculated for gas phase using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with 6-311++G(d,p) basis set. The diversity in molecular geometry of fluorophenyl substituted thiosemicarbazones has been discussed based on the X-ray crystal structure reports and theoretical calculation results from the literature. The assignments of the vibrational frequencies have been done on the basis of potential energy distribution (PED) analysis by using VEDA4 software. A good correlation was found between the computed and experimental geometric and vibrational data. In addition, the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbital energy levels and other related molecular energy values of the compound have been determined using the same level of theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. A facile approach towards synthesis, characterization, single crystal structure, and DFT study of 5-bromosalicylalcohol

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Rupali, E-mail: rastogirupali@ymail.com [ITM University, Department of Chemistry (India); Tarannum, Nazia [Ch. Charan Singh University, Department of Chemistry (India); Butcher, R. J. [Howard University, Chemistry Department (United States)

    2016-03-15

    5-Bromosalicylalcohol was prepared by the interaction of NaBH{sub 4} and 5-bromosalicylaldehyde. The use of sodium borohydride makes the reaction easy, facile, economic and does not require any toxic catalyst. The compound is characterized by FTIR, {sup 1}H NMR, {sup 13}C NMR, TEM and ESI-mass spectra. Crystal structure is determined by single crystal X-ray analysis. Quantum mechanical calculations of geometries, energies and thermodynamic parameters are carried out using density functional theory (DFT/B3LYP) method with 6-311G(d,p) basis set. The optimized geometrical parameters obtained by B3LYP method show good agreement with experimental data.

  9. Fast isotropic banding-free bSSFP imaging using 3D dynamically phase-cycled radial bSSFP (3D DYPR-SSFP)

    Energy Technology Data Exchange (ETDEWEB)

    Benkert, Thomas; Blaimer, Martin; Breuer, Felix A. [Research Center Magnetic Resonance Bavaria (MRB), Wuerzburg (Germany); Ehses, Philipp [Tuebingen Univ. (Germany). Dept. of Neuroimaging; Max Planck Institute for Biological Cybernetics, Tuebingen (Germany). High-Field MR Center; Jakob, Peter M. [Research Center Magnetic Resonance Bavaria (MRB), Wuerzburg (Germany); Wuerzburg Univ. (Germany). Dept. of Experimental Physics 5

    2016-05-01

    Aims: Dynamically phase-cycled radial balanced steady-state free precession (DYPR-SSFP) is a method for efficient banding artifact removal in bSSFP imaging. Based on a varying radiofrequency (RF) phase-increment in combination with a radial trajectory, DYPR-SSFP allows obtaining a banding-free image out of a single acquired k-space. The purpose of this work is to present an extension of this technique, enabling fast three-dimensional isotropic banding-free bSSFP imaging. Methods: While banding artifact removal with DYPR-SSFP relies on the applied dynamic phase-cycle, this aspect can lead to artifacts, at least when the number of acquired projections lies below a certain limit. However, by using a 3D radial trajectory with quasi-random view ordering for image acquisition, this problem is intrinsically solved, enabling 3D DYPR-SSFP imaging at or even below the Nyquist criterion. The approach is validated for brain and knee imaging at 3 Tesla. Results: Volumetric, banding-free images were obtained in clinically acceptable scan times with an isotropic resolution up to 0.56 mm. Conclusion: The combination of DYPR-SSFP with a 3D radial trajectory allows banding-free isotropic volumetric bSSFP imaging with no expense of scan time. Therefore, this is a promising candidate for clinical applications such as imaging of cranial nerves or articular cartilage.

  10. Vibrational absorption spectra, DFT and SCC-DFTB conformational study and analysis of [Leu]enkephalin

    DEFF Research Database (Denmark)

    Abdali, Salim; Niehaus, T.A.; Jalkanen, Karl J.

    2003-01-01

    . Ab initio (DFT at the B3LYP/6-31G* level of theory) and semi-empirical (SCC-DFTB) with and without dispersion correction were applied to simulate the VA spectra of [Leu] enkephalin. In these calculations structures taken from X-ray measurements for different conformers of the molecule were used...

  11. STUDI KOMPUTASI BERBASIS DFT TERHADAP FENOMENA QUANTUM TUNNELING DALAM ISOMERISASI METILHIDROKSIKARBENA

    Directory of Open Access Journals (Sweden)

    Jumaidil Awal

    2016-01-01

    Full Text Available Density functional theory-based methods have been applied to predict the most possible one among the isomerizations of methylhydroxycarbene considering the probability of hydrogen tunneling occurrence. B3LYP/6-31+G(d,p and M08-SO/6-31+G(d,p methods were applied in all computations using GAMESS-US software. There were three steps of computation in this research. First, electronic structure computations of both equilibrium and transition compounds involved in all isomerization alternatives in order to obtain the optimum structures of the compounds. Second, vibrational computations of optimum transition structures to ensure that each of the respective structures is well on its potential energy surface. Third, tunneling analysis accomplished by intrinsic reaction coordinate (IRC computatuins for all isomerization alternatives followed by tunneling probabilitycalculation using the Wentzel-Kramers-Brillouin (WKB formula for methylhydroxycarbene isomerizations. The result of this research showed that the DFT methods successfully produced the optimum structure of each compound. Both DFT methods also successfully mapped all the intrinsic reaction coordinates. B3LYP/6-31+G(d,p method gave tunneling probabilities of 3.55 x 10-19 for the isomerization into acetaldehyde and 3.30 x 10-20 for that into vinyl alcohol. While M08-SO/6-31+G(d,p method gave tunneling probabilities of 2.38 x 10-23 for the isomerization into acetaldehyde and 4.79 x 10-23 for that into vinyl alcohol. Keywords: DFT, methylhydroxycarbene, hydrogen tunneling, isomerization

  12. Investigating actinide compounds within a hybrid MCSCF-DFT model

    International Nuclear Information System (INIS)

    Fromager, E.; Jensen, H.J.A.; Wahlin, P.; Real, F.; Wahlgren, U.

    2007-01-01

    Complete text of publication follows: Investigations of actinide chemistry with quantum chemical methods still remain a complicated task since it requires an accurate and efficient treatment of the environment (crystal or solvent) as well as relativistic and electron correlation effects. Concerning the latter, the current correlated methods, based on either Density-Functional Theory (DFT) or Wave-Function Theory (WFT), have their advantages and drawbacks. On the one hand, Kohn-Sham DFT (KS-DFT) calculates the dynamic correlation quite accurately and at a fairly low computational cost. However, it does not treat adequately the static correlation, which is significant in some actinide compounds because of the near-degeneracy of the 5f orbitals: a first example is the bent geometry obtained in KS-DFT(B3LYP) for the neptunyl ion NpO 2 3+ , which is found to be linear within a Multi-Configurational Self-Consistent Field (MCSCF) model [1]. A second one is the stable and bent geometry obtained in KS-DFT(B3LYP) for the plutonyl ion PuO 2 4+ , which disintegrates at the MCSCF level [1]. On the other hand, WFT can describe the static correlation, using for example a MCSCF model, but then an important part of the dynamic correlation has to be neglected. This can be recovered with perturbation-theory based methods like for example CASPT2 or NEVPT2, but their computational complexity prevents large scale calculations. It is therefore of great interest to develop a hybrid MCSCF-DFT model which combines the best of both WFT and DFT approaches. The merge of WFT and DFT can be achieved by splitting the two-electron interaction into long-range and short-range parts [2]. The long-range part is then treated by WFT and the short-range part by DFT. We use the so-called 'erf' long-range interaction erf(μr 12 )/r 12 , which is based on the standard error function, and where μ is a free parameter which controls the long/short-range decomposition. The newly proposed recipe for the

  13. DFT study of conformational and vibrational characteristics of 2-(2-hydroxyphenyl)benzothiazole molecule.

    Science.gov (United States)

    Pandey, Urmila; Srivastava, Mayuri; Singh, R P; Yadav, R A

    2014-08-14

    The conformational and IR and Raman spectral studies of 2-(2-hydroxyphenyl)benzothiazole have been carried out by using the DFT method at the B3LYP/6-311++G(**) level. The detailed vibrational assignments have been done on the basis of calculated potential energy distributions. Comparative studies of molecular geometries, atomic charges and vibrational fundamentals of all the conformers have been made. There are four possible conformers for this molecule. The optimized geometrical parameters obtained by B3LYP/6-311++G(**) method showed good agreement with the experimental X-ray data. The atomic polar tensor (APT) charges, Mulliken atomic charges, natural bond orbital (NBO) analysis and HOMO-LUMO energy gap of HBT and its conformers were also computed. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. DFT study on the isomerization and tautomerism in vitamins B3 (niacin), B5 (pantothenic acid) and B7 (biotin)

    Science.gov (United States)

    Valadbeigi, Younes; Farrokhpour, Hossein; Tabrizchi, Mahmoud

    2014-05-01

    Isomerization and tautomerism of the three water soluble vitamins including B3, B5 and B7 were studied applying density functional theory using B3LYP method in gas and aqueous phases. Activation energies (Ea), Gibbs free energies of activation (ΔG#), and imaginary frequencies of the transition state structures were calculated for all the isomerization and tautomerism reactions. Activation energies of the neutral → zwitterion (amine-enamine) tautomerism in vitamin B3 were 310-360 kJ/mol where these values for the keto-enol tautomerism were 100-130 kJ/mol. It was found that water molecule catalyzes the tautomerism and decreases the activation energies about 90-160 kJ/mol.

  15. An extended hybrid density functional (X3LYP) with improved descriptions of nonbond interactions and thermodynamic properties of molecular systems

    OpenAIRE

    Xu, Xin; Zhang, Qingsong; Muller, Richard P.; Goddard, William A., III

    2005-01-01

    We derive here the form for the exact exchange energy density for a density that decays with Gaussian-type behavior at long range. This functional is intermediate between the B88 and the PW91 exchange functionals. Using this modified functional to match the form expected for Gaussian densities, we propose the X3LYP extended functional. We find that X3LYP significantly outperforms Becke three parameter Lee–Yang–Parr (B3LYP) for describing van der Waals and hydrogen bond interactions, while per...

  16. Benchmarking DFT and TD-DFT Functionals for the Ground and Excited States of Hydrogen-Rich Peptide Radicals.

    Science.gov (United States)

    Riffet, Vanessa; Jacquemin, Denis; Cauët, Emilie; Frison, Gilles

    2014-08-12

    We assess the pros and cons of a large panel of DFT exchange-correlation functionals for the prediction of the electronic structure of hydrogen-rich peptide radicals formed after electron attachment on a protonated peptide. Indeed, despite its importance in the understanding of the chemical changes associated with the reduction step, the question of the attachment site of an electron and, more generally, of the reduced species formed in the gas phase through electron-induced dissociation (ExD) processes in mass spectrometry is still a matter of debate. For hydrogen-rich peptide radicals in which several positive groups and low-lying π* orbitals can capture the incoming electron in ExD, inclusion of full Hartree-Fock exchange at long-range interelectronic distance is a prerequisite for an accurate description of the electronic states, thereby excluding several popular exchange-correlation functionals, e.g., B3LYP, M06-2X, or CAM-B3LYP. However, we show that this condition is not sufficient by comparing the results obtained with asymptotically correct range-separated hybrids (M11, LC-BLYP, LC-BPW91, ωB97, ωB97X, and ωB97X-D) and with reference CASSCF-MRCI and EOM-CCSD calculations. The attenuation parameter ω significantly tunes the spin density distribution and the excited states vertical energies. The investigated model structures, ranging from methylammonium to hexapeptide, allow us to obtain a description of the nature and energy of the electronic states, depending on (i) the presence of hydrogen bond(s) around the cationic site(s), (ii) the presence of π* molecular orbitals (MOs), and (iii) the selected DFT approach. It turns out that, in the present framework, LC-BLYP and ωB97 yields the most accurate results.

  17. Structure and Absolute Configuration of Ginkgolide B Characterized by IR- and VCD Spectroscopy

    DEFF Research Database (Denmark)

    Andersen, Niels Højmark; Christensen, N.J.; Lassen, Peter Rygaard

    2010-01-01

    Experimental and calculated (B3LYP/6-31G(d)) vibrational Circular dichroism (VCD) and IR spectra are compared, illustrating that the structure and absolute configuration of ginkgolide B (GB) may be characterized directly in solution. A conformational search for GB using MacroModel and subsequent...... DFT optimizations (B3LYP/6-31G(d)) provides a structure for the lowest energy conformer which agrees well with the structure determined by X-ray diffraction. In addition, a conformer at all energy of 7 kJ mol(-1) (B3LYP/6-311+G(2d,2p)) with respect to the lowest energy conformer is predicted...

  18. Hydrogen bonding interactions in PN...HX complexes: DFT and ab initio studies of structure, properties and topology.

    Science.gov (United States)

    Varadwaj, Pradeep Risikrishna

    2010-05-01

    Spin-restricted DFT (X3LYP and B3LYP) and ab initio (MP2(fc) and CCSD(fc)) calculations in conjunction with the Aug-CC-pVDZ and Aug-CC-pVTZ basis sets were performed on a series of hydrogen bonded complexes PN...HX (X = F, Cl, Br) to examine the variations of their equilibrium gas phase structures, energetic stabilities, electronic properties, and vibrational characteristics in their electronic ground states. In all cases the complexes were predicted to be stable with respect to the constituent monomers. The interaction energy (Delta E) calculated using a super-molecular model is found to be in this order: PN...HF > PN...HCl > PN...HBr in the series examined. Analysis of various physically meaningful contributions arising from the Kitaura-Morokuma (KM) and reduced variational space self-consistent-field (RVS-SCF) energy decomposition procedures shows that the electrostatic energy has significant contribution to the over-all interaction energy. Dipole moment enhancement (Delta mu) was observed in these complexes expected of predominant dipole-dipole electrostatic interaction and was found to follow the trend PN...HF > PN...HCl > PN...HBr at the CCSD level. However, the DFT (X3LYP and B3LYP) and MP2 levels less accurately determined these values (in this order HF 0, nabla(2)rho(c) > 0 and H(c) > 0 at the BCP) whilst the bonds in PN (rho(c) > 0, nabla(2)rho(c) > 0 and H(c) 0, nabla(2)rho(c) BD*(HX) delocalization.

  19. Cooperativity effect involving drug-DNA/RNA intermolecular interaction: A B3LYP-D3 and MP2 theoretical investigation on ketoprofen⋯cytosine⋯H2O system.

    Science.gov (United States)

    Zhen, Jun-Ping; Wei, Xiao-Chun; Shi, Wen-Jing; Huang, Zhu-Yuan; Jin, Bo; Zhou, Yu-Kun

    2017-11-14

    In order to examine the origin of the drug action and design new DNA/RNA-targeted drugs, the cooperativity effect involving drug-DNA/RNA intermolecular interaction in ketoprofen⋯cytosine⋯H 2 O ternary system were investigated by the B3LYP, B3LYP-D3, and MP2 methods with the 6-311++G(2d,p) basis set. The thermodynamic cooperativity was also evaluated at 310.15 K. The N-H⋯O, O-H⋯O, O-H⋯N, C-H⋯N, and C-H⋯O H bonds coexist in ternary complexes. The intermolecular interactions obtained by B3LYP-D3 are close to those calculated by MP2. The steric effects and van der Waals interactions have little influence on the cooperativity effects. The anti-cooperativity effect in ket⋯cyt⋯H 2 O is far more notable than the cooperativity effect, and the stability of the cyclic structure with anti-cooperativity effect is higher than that of the linear structure with cooperativity effect, as is confirmed by the AIM (atoms in molecules) and RDG (reduced density gradient) analysis. Thus, it can be inferred that, in the presence of H 2 O, the anti-cooperativity effect plays a dominant role in the drug-DNA/RNA interaction, and the nature of the hydration in the binding of drugs to DNA/RNA bases is the H-bonding anti-cooperativity effect. Furthermore, the drug always links simultaneously with DNA/RNA base and H 2 O, and only in this way can the biological activity of drugs play a role. In most cases, the enthalpy change is the major factor driving the cooperativity, as is different from most of biomacromolecule complexes.

  20. Theoretical Study of 1,3-Dipolar Cycloadditions Regioselectivity of Benzyl Azide with Glycosyl-O Acetylene Using Density Functional Theory (DFT

    Directory of Open Access Journals (Sweden)

    Adib Ghaleb

    2017-12-01

    Full Text Available A theoretical study of 1,3-cycloaddition has been carried out using density functional theory (DFT methods at the B3LYP/6-31G* level. The regioselectivity of the reaction have been clarified through different theoretical approaches: Case of a Two-Center Process (Domingo approach, HSAB principle (Gazquez and Mendez approach, and the activation energy calculations. The analysis of results shows that the reaction takes place along concerted asynchronous mechanism and the isomer meta is favored, in agreement with the experiment results. DOI: http://dx.doi.org/10.17807/orbital.v9i5.1017 

  1. Vibrational, DFT, thermal and dielectric studies on 3-nitrophenol-1,3,5-triazine-2,4,6-triamine (2/1)

    Science.gov (United States)

    Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Marchewka, M. K.; Gunasekaran, S.; Anbalagan, G.

    2014-01-01

    A new organic-organic salt, 3-nitrophenol-1,3,5-triazine-2,4,6-triamine (2/1) (3-NPM) has been synthesized by slow evaporation technique at room temperature. Single crystal X-ray diffraction analysis reveals that 3-NPM crystallizes in orthorhombic system with centrosymmetric space group Pbca and the lattice parameters are a = 15.5150(6) Å, b = 12.9137(6) Å, c = 17.8323(6) Å, α = β = γ = 90° and V = 3572.8(2) (Å)3. The geometry, fundamental vibrational frequencies are interpreted with the aid of structure optimization and normal coordinate force field calculations based on density functional theory (DFT) B3LYP/6-311G(d,p) method. IR and Raman spectra of 3-NPM have been recorded and analyzed. The complete vibrational assignments are made on the basis of potential energy distribution (PED). The electric dipole moment, polarizability and the first order hyperpolarizability values of the 3-NPM have been calculated. 1H and 13C NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP method with 6-311G (d,p) basis set. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties are performed. Mulliken and Natural charges of the title molecule are also calculated and interpreted. Thermal decomposition behavior of 3-NPM has been studied by means of thermogravimetric analysis. The dielectric measurements on the powdered sample have been carried out and the variation of dielectric constant and dielectric loss at different frequencies of the applied field has been studied and the results are discussed in detail.

  2. Molecular Structure, Spectroscopic and DFT Computational Studies of Arylidene-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H-trione

    Directory of Open Access Journals (Sweden)

    Assem Barakat

    2016-09-01

    Full Text Available Reaction of barbituric acid derivatives and di-substituted benzaldehyde in water afforded arylidene-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H-trione derivatives (1 and 2. The one step reaction proceeded efficiently, smoothly, and in excellent yield. The arylidene compounds were characterized by spectrophotometric tools plus X-ray single crystal diffraction technique. Quantum chemical calculations were performed using the DFT/B3LYP method to optimize the structure of the two isomers (1 and 2 in the gas phase. The optimized structures were found to agree well with the experimental X-ray structure data. The highest occupied (HOMO and lowest unoccupied (LUMO frontier molecular orbitals analyses were performed and the atomic charges were calculated using natural populationanalysis.

  3. Synthesis, structural characterization, and DFT calculations of 3-buthyl-4-(3-methyl-3-mesitylcyclobut-1-yl)-1,3-thiazole-2(3H)-thione

    Energy Technology Data Exchange (ETDEWEB)

    Şen, B. [Dokuz Eylül University, Department of Physics, Faculty of Science (Turkey); Barim, E.; Kirilmis, C. [Adıyaman University, Department of Chemistry, Faculty of Art and Science (Turkey); Aygün, M., E-mail: muhittin.aygun@deu.edu.tr [Dokuz Eylül University, Department of Physics, Faculty of Science (Turkey)

    2016-03-15

    The title compound, C{sub 21}H{sub 29}NS{sub 2}, has been synthesized and its crystal structure has been determined from single crystal X-ray diffraction data. Crystals are monoclinic, a = 11.4923(8), b = 13.1842(7), c = 14.6583(8) Å, β = 109.983(6)°, sp. gr. P2{sub 1}/c, Z = 4. Mesityl and thiazole groups are in cis positions with respect to the cyclobutane ring. The cyclobutane ring is puckered, with a dihedral angle of 26.6(2)° between the two three-atom planes. The crystal structure involves one weak intermolecular C–H···S hydrogen-bond. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d, p) basis set in ground state. Geometric parameters (bond lengths, bond angles and torsion angles) and vibrational assignments have been calculated theoretically and compared with the experimental data.

  4. Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules.

    Science.gov (United States)

    Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Adamo, Carlo

    2009-09-08

    Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (∼500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated. Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22% and 25% of exact exchange (X3LYP, B98, PBE0, and mPW1PW91) and, on the other hand, a long-range-corrected hybrid with a less-rapidly increasing HF ratio, namely LC-ωPBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3LYP schemes deliver fairly small deviations but do not outperform standard hybrids such as X3LYP or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 eV, though the errors significantly depend on the subset of molecules or states considered. As an illustration, PBE0 and LC-ωPBE(20) provide a mean absolute error of only 0.14 eV for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.

  5. The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties

    Science.gov (United States)

    Xu, Xin; Goddard, William A.

    2004-01-01

    We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee–Yang–Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee–Yang–Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA. PMID:14981235

  6. Characterization of Meldrum's acid derivative 5-(5-Ethyl-1,3,4-thiadiazol-2-ylamino)methylene-2,2-dimethyl-1,3-dioxane-4,6-dione by Raman and FT-IR spectroscopy and DFT calculations

    Science.gov (United States)

    de Toledo, T. A.; da Silva, L. E.; Teixeira, A. M. R.; Freire, P. T. C.; Pizani, P. S.

    2015-07-01

    In this study, the structural and vibrational properties of Meldrum's acid derivative 5-(5-Ethyl-1,3,4-thiadiazol-2-ylamino)methylene-2,2-dimethyl-1,3-dioxane-4,6-dione, C11H13N3O4S were studied combining experimental techniques such as Raman and FT-IR spectroscopy and density functional theory (DFT) calculations. The Raman and FT-IR spectra were recorded at room conditions in the regions from 80 to 3400 cm-1 and 400 to 4000 cm-1, respectively. Vibrational wavenumbers were predicted using DFT calculations with the hybrid functional B3LYP and basis set 6-31G(d,p). A comparison between experimental and theoretical data is provided for the Raman and FT-IR spectra. The descriptions of the normal modes were carried by means of potential energy distribution (PED).

  7. Vibrational dynamics (IR, Raman, NRVS) and DFT study of new antitumor tetranuclearstannoxanecluster, Sn(IV)$-$oxo$-${di$-$o$-$vanillin} dimethyl dichloride

    Energy Technology Data Exchange (ETDEWEB)

    Arjmand, F. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Sharma, S. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Usman, M. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Leu, B. M. [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Hu, M. Y. [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Toupet, L. [Univ. de Rennes, Rennes (France). Inst. de Physique de Rennes; Gosztola, David J. [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Tabassum, S. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry

    2016-06-21

    The vibrational dynamics of a newly synthesized tetrastannoxane was characterized with a combination of experimental (Raman, IR and tin-based nuclear resonance vibrational spectroscopy) and computational (DFT/B3LYP) methods, with an emphasis on the vibrations of the tin sites. The cytotoxic activity revealed a significant regression selectively against the human pancreatic cell lines.

  8. Thiol-thione tautomeric analysis, spectroscopic (FT-IR, Laser-Raman, NMR and UV-vis) properties and DFT computations of 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiol molecule.

    Science.gov (United States)

    Gökce, Halil; Öztürk, Nuri; Ceylan, Ümit; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan

    2016-06-15

    In this study, the 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiol molecule (C7H6N4S) molecule has been characterized by using FT-IR, Laser-Raman, NMR and UV-vis spectroscopies. Quantum chemical calculations have been performed to investigate the molecular structure (thione-thiol tautomerism), vibrational wavenumbers, electronic transition absorption wavelengths in DMSO solvent and vacuum, proton and carbon-13 NMR chemical shifts and HOMOs-LUMOs energies at DFT/B3LYP/6-311++G(d,p) level for all five tautomers of the title molecule. The obtained results show that the calculated vibrational wavenumbers, NMR chemical shifts and UV-vis wavelengths are in a good agreement with experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Synthesis, spectroscopic and DFT studies of novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid

    Science.gov (United States)

    Devi, Poornima; Fatma, Shaheen; Bishnoi, Abha; Srivastava, Krishna; Shukla, Shraddha; Kumar, Roop

    2018-04-01

    A novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid has been synthesized and its structural elucidation has been done by UV, FT-IR, 1H and 13C NMR spectroscopy. All quantum chemical calculations were carried out at level of density functional theory (DFT) with B3LYP function using 6-31G (d, p) basis atomic set. AIM approach has been incorporated for the analysis of various intermolecular interactions. Polarizability and hyperpolarizabilities values have been calculated along with the exploration of nonlinear optical properties of the title compound. DFT computed total first static hyperpolarizability (β0 = 0.2747 × 10-30 esu) indicates that title molecule could be an area of interest as an attractive future NLO material. For the analysis of thermal behaviour of title molecule, thermodynamic properties such as heat capacity, entropy and enthalpy change at various temperatures have been calculated. The NBO computations were done for the correlation of possible transitions with the electronic transitions. Electrophilic and nucleophilic regions were identified with the help of MESP plot. Determination of energy gap has been done by using HOMO and LUMO energy values, along with the computation of electronegativity and electrophilicity indices.

  10. Effect of methyl substituents on the electronic transitions in simple meso-aniline-BODIPY based dyes: RI-CC2 and TD-CAM-B3LYP computational investigation

    Science.gov (United States)

    Petrushenko, Igor K.; Petrushenko, Konstantin B.

    2018-02-01

    The S0 → Si, i = 1-5 electronic transitions of four 8-(4-aniline)-BODIPY and four 8-(N,N-dimethyl)-BODIPY dyes, differ by number and position of methyl substituents in the BODIPY frame, were investigated theoretically using ab initio the coupled cluster doubles (CC2) and TD-CAM-B3LYP methods. Methyl substituents in the BODIPY frame and the aniline fragment at the meso position disturb energy of local excitations S0 → S1, S0 → S3, and S0 → S4 weakly in comparison with the fully unsubstituted BODIPY molecule. These transitions in experimental spectra form the most long-wave absorption bands at ca. 500 nm as well as absorption bands in the region of 300-400 nm. At the same time, the presence of aniline fragments leads to the appearance of new S0 → S2 transitions of the charge transfer character in electronic spectra of BODIPYs. We also found a linear relationship between vertical energy of these charge transfer transitions and the electron donating power of an aniline fragment and electron accepting power of the BODIPY core depending on the number and position of methyl groups. The CC2 method provides the best overall description of the excitation energies in line with the experimental observations. On average, the quality of TD-CAM-B3LYP is almost equal to that of CC2, however the TD method with the CAM-B3LYP functional slightly underestimates the CT excitation energy.

  11. Crystal structure, spectral property, antimicrobial activity and DFT calculation of N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea

    Science.gov (United States)

    Zhang, Hong-Song; Zhang, Kong-Yan; Chen, Li-Chuan; Li, Yao-Xin; Chai, Lan-Qin

    2017-10-01

    N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea was synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR, UV-Vis and emission spectroscopy, as well as by single-crystal X-ray diffraction. X-ray crystallographic analyses have indicated that the crystal structure consists of two dimethyl sulfoxide (DMSO) solvent molecules and the structural geometry of DMSO is a trigonal pyramid in shape. In the crystal structure, a self-assembling two-dimensional (2-D) layer supramolecular architecture is formed through intermolecular hydrogen bonds, Cdbnd O···π (thiadiazole ring) and π···π stacking interactions. The geometry of the compound has been optimized by the DFT method and the results are compared with the X-ray diffraction data. The electronic transitions and spectral features of the compound were carried out by using DFT/B3LYP method. In addition, the antimicrobial activity was also studied, and the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and HOMO-LUMO gap were also calculated.

  12. Structural analysis of flavonoids in solution through DFT 1H NMR chemical shift calculations: Epigallocatechin, Kaempferol and Quercetin

    Science.gov (United States)

    De Souza, Leonardo A.; Tavares, Wagner M. G.; Lopes, Ana Paula M.; Soeiro, Malucia M.; De Almeida, Wagner B.

    2017-05-01

    In this work, we showed that comparison between experimental and theoretical 1H NMR chemical shift patterns, calculated using Density Functional Theory (DFT), can be used for the prediction of molecular structure of flavonoids in solution, what is experimentally accessible for gas phase (electron diffraction methods) and solid samples (X-ray diffraction). The best match between B3LYP/6-31G(d,p)-PCM 1H NMR calculations for B ring rotated structures and experimental spectra can provide information on the conformation adopted by polyphenols in solution (usually DMSO-d6, acetone-d6 as solvents), which may differ from solid state and gas phase observed structures, and also DFT optimized geometry in the vacuum.

  13. Benchmarking quantum mechanical calculations with experimental NMR chemical shifts of 2-HADNT

    Science.gov (United States)

    Liu, Yuemin; Junk, Thomas; Liu, Yucheng; Tzeng, Nianfeng; Perkins, Richard

    2015-04-01

    In this study, both GIAO-DFT and GIAO-MP2 calculations of nuclear magnetic resonance (NMR) spectra were benchmarked with experimental chemical shifts. The experimental chemical shifts were determined experimentally for carbon-13 (C-13) of seven carbon atoms for the TNT degradation product 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT). Quantum mechanics GIAO calculations were implemented using Becke-3-Lee-Yang-Parr (B3LYP) and other six hybrid DFT methods (Becke-1-Lee-Yang-Parr (B1LYP), Becke-half-and-half-Lee-Yang-Parr (BH and HLYP), Cohen-Handy-3-Lee-Yang-Parr (O3LYP), Coulomb-attenuating-B3LYP (CAM-B3LYP), modified-Perdew-Wang-91-Lee-Yang-Parr (mPW1LYP), and Xu-3-Lee-Yang-Parr (X3LYP)) which use the same correlation functional LYP. Calculation results showed that the GIAO-MP2 method gives the most accurate chemical shift values, and O3LYP method provides the best prediction of chemical shifts among the B3LYP and other five DFT methods. Three types of atomic partial charges, Mulliken (MK), electrostatic potential (ESP), and natural bond orbital (NBO), were also calculated using MP2/aug-cc-pVDZ method. A reasonable correlation was discovered between NBO partial charges and experimental chemical shifts of carbon-13 (C-13).

  14. Synthetic scope and DFT analysis of the chiral binap–gold(I complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

    Directory of Open Access Journals (Sweden)

    María Martín-Rodríguez

    2013-11-01

    Full Text Available The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(Sa-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

  15. The effect of the fused-ring substituent on anthracene chalcones: crystal structural and DFT studies of 1-(anthracen-9-yl-3-(naphthalen-2-ylprop-2-en-1-one and 1-(anthracen-9-yl-3-(pyren-1-ylprop-2-en-1-one

    Directory of Open Access Journals (Sweden)

    Dian Alwani Zainuri

    2018-05-01

    Full Text Available The title chalcone compounds, C27H18O (I and C33H20O (II, were synthesized using a Claisen–Schmidt condensation. Both compounds display an s-trans configuration of the enone moiety. The crystal structures feature intermolecular C—H...O and C—H...π interactions. Quantum chemical analysis of density functional theory (DFT with a B3LYP/6–311++G(d,p basis set has been employed to study the structural properties of the compound. The effect of the intermolecular interactions in the solid state are responsible for the differences between the experimental and theoretical optimized geometrical parameters. The small HOMO–LUMO energy gap in (I (exp : 3.18 eV and DFT: 3.15 eV and (II (exp : 2.76 eV and DFT: 2.95 eV indicates the suitability of these compounds for optoelectronic applications. The intermolecular contacts and weak contributions to the supramolecular stabilization are analysed using Hirshfeld surface analysis.

  16. Conformational, vibrational spectroscopic and quantum chemical studies on 5-methoxyindole-3-carboxaldehyde: A DFT approach

    Science.gov (United States)

    Jeyaseelan, S. Christopher; Hussain, Shamima; Premkumar, R.; Rekha, T. N.; Benial, A. Milton Franklin

    2018-04-01

    Indole and its derivatives are considered as good ligands for various disease causing proteins in human because of presence of the single nitrogen atom. In the present study, the potential energy surface scan was performed for the most stable molecular structure of the 5-Methoxyindole-3-carboxaldehyde (MICA) molecule. The most stable molecular structure was optimized by DFT/B3LYP method with 6-311G++ (d, p) basis set using Gaussian 09 program package. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculations using VEDA 4.0 program. The Frontier molecular orbitals analysis was performed and related molecular propertieswere calculated. The possible electrophilic and nucleophilic reactive sites of the molecule were studied using molecular electrostatic potential analysis, which confirms the bioactivity of the molecule. The natural bond orbital analysis was also performed to confirm the bioactivity of the title molecule.

  17. Study of a Conformational Equilibrium of Lisinopril by HPLC, NMR, and DFT

    Directory of Open Access Journals (Sweden)

    Sondes Bouabdallah

    2014-01-01

    Full Text Available The isomerization of lisinopril has been investigated using chromatographic, NMR spectroscopic, and theoretical calculations. The NMR data, particularly the NOEDIFF experiments, show that the major species that was eluted first is the trans form. The proportion was 77% and 23% for the trans and cis, respectively. The thermodynamic parameters (ΔH, ΔS, and ΔG were determined by varying the temperature in the NMR experiments. The interpretations of the experimental data were further supported by DFT/B3LYP calculations.

  18. Study on the noncoincidence effect phenomenon using matrix isolated Raman spectra and the proposed structural organization model of acetone in condense phase

    Science.gov (United States)

    Xu, Wenwen; Wu, Fengqi; Zhao, Yanying; Zhou, Ran; Wang, Huigang; Zheng, Xuming; Ni, Bukuo

    2017-03-01

    The isotropic and anisotropic Raman spectra of acetone and deuterated acetone isolated in an argon matrix have been recorded for the understanding of noncoincidence effect (NCE) phenomenon. According to the matrix isolated Raman spectra and DFT calculations, we proposed aggregated model for the explanations of the acetone C=O vibration NCE phenomenon and its concentration effect. The experimental data were in consistence with the DFT calculations performed at the B3LYP-D3/6-311 G (d,p) levels based on the proposed model. The experimental identification of the monomer, dimer and trimer are reported here, and the dynamic of the transformation from monomer to aggregated structure can be easily controlled by tuning annealing temperature.

  19. From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties

    Science.gov (United States)

    Xu, Xin; Goddard, William A., III

    2004-03-01

    We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA.

  20. Synthesis and DFT calculations of some 2-aminothiazoles

    Science.gov (United States)

    Rezania, Jafar; Behzadi, Hadi; Shockravi, Abbas; Ehsani, Morteza; Akbarzadeh, Elahe

    2018-04-01

    A series of 2-aminothiazole derivatives have been synthesized by the reaction of acetyl compounds with thiourea and iodine as catalyst under solvent-free condition, a green chemistry method. The quantum chemical calculations at the DFT/B3LYP level of theory in gas phase were carried out for starting acetyl derivatives. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and related reactivity descriptor of acetyl derivatives, as well as, enthalpy of reactions are calculated in order to investigate the reaction properties of acetyl compounds and yields of the reactions. The calculated reactivity descriptors are well correlated to activity of different acetyl derivatives.

  1. Molecular interactions in the complexes of toluene with butyronitrile: A DFT approach

    Science.gov (United States)

    Karthick, N. K.; Arivazhagan, G.

    2018-04-01

    Density Functional Theory (DFT) has been employed to investigate the self association of butyronitrile and the heterointeractions in the 1:2 (toluene: butyronitrile) and 1:1 complexes of toluene with butyronitrile. For this investigation the B3LYP functional with Grimme's dispersion correction (D3) term and ωB97XD functionals were used. The theoretical frequency analysis shows the unsuitability of B3LYP with D3 for the present investigation. Therefore, Natural Bonding Orbital analysis was done at the functional ωB97XD. It is found through this work that only the methylene hydrogens of butyronitrile are responsible for the self association among the butyronitrile molecules. In 1:1 complex, the red shift in the butyronitrile methyl asymmetric stretching mode is not due to the active participation of this group in heterointeractions and it is solely due to the other interactions happening in its vicinity. Only the interaction (TOL) C - H ⋯ N(BN) is present in the complex. In 1:2 complex the butyronitrile methyl/methylene hydrogens interact with the delocalized electron cloud of toluene and the toluene hydrogens interact with the butyronitrile nitrogen. Comparison of interaction energies shows that the stability of 1:2 complex is more than that of butyronitrile dimer and 1:1 complex.

  2. The study of structural characteristic of yttrium(3+) aquaion by density functional methods

    International Nuclear Information System (INIS)

    Buz'ko, V.Yu.; Sukhno, I.V.; Polushin, A.A.; Panyushkin, V.T.

    2006-01-01

    Structural characteristics of the yttrium aquaion Y(H 2 O) 8 3+ are calculated by DFT technique using density functionals SVWN5, B3LYP, B3P86, O3LYP, B3PW91, B1LYP, B971, MPW1PW9, PBE1PBE, BHandH and BNandHLYP. All calculations are carried out by means of GAUSSIAN-03 code. Structural characteristics of the Y(H 2 O) 8 3+ aquaion obtained by the use of the density functional method agree satisfactorily with the experiment. Hybrid nonlocal GGA-functionals foretell worse the structural characteristics of the Y(H 2 O) 8 3+ aquaion as compared with the reasonable simple combined functional BHandH and the simplest functional SVWN5 of the LSDA theory [ru

  3. Electronic structure, hydrogen bonding and spectroscopic profile of a new 1,2,4-triazole-5(4H)-thione derivative: A combined experimental and theoretical (DFT) analysis

    Science.gov (United States)

    Al-Tamimi, Abdul-Malek S.

    2016-09-01

    Density functional theory has been implemented to study the electronic structure, molecular properties and vibrational spectra of 3-(adamantan-1-yl)-4-(4-chlorophenyl)-1H-1,2,4-triazole-5(4H)-thione, a novel 1,2,4-triazole-5(4H)-thione derivative. Hydrogen bonded dimer of the title molecule has been studied using B3LYP, M06-2X and X3LYP functionals at 6-311++ G(d,p) level of theory. The intermolecular hydrogen bonding has been studied using NBO analysis of the dimer. Bader's AIM theory was also used to evaluate the strength as well as the hydrogen bonding characteristics. Experimental FT-IR and FT-Raman spectra of the title molecule were related with the spectral data obtained with DFT/B3LYP method. The 1H NMR chemical shifts of the title molecule were calculated by the GIAO method and compared with experimental results. Dipole moment, polarizability (α), first order static hyperpolarizability (β) along with molecular electrostatic potential surface have been calculated. Frequency-dependent first hyperpolarizabilities, β(-2ω;ω,ω) and β(-ω;ω,0) have also been evaluated to study the non-linear optical behavior of the title compound. UV-Vis spectrum of the title molecule was recorded and TD-DFT method has been used to calculate six lowest excited states and the corresponding excitation energies.

  4. Characterisation of 1,3-diammonium propylselenate monohydrate by XRD, FT-IR, FT-Raman, DSC and DFT studies

    Science.gov (United States)

    Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.; Atalay, Yusuf

    2016-03-01

    The crystals of 1,3-diammonium propylselenate monohydrate (DAPS) were prepared and characterised X-ray diffraction (XRD), FT-IR, FT-Raman spectroscopy, and DFT/B3LYP methods. It comprises protonated propyl ammonium moieties (diammonium propyl cations), selenate anions and water molecule which are held together by a number of hydrogen bonds and form infinite chains. The XRD data confirm the transfer of two protons from selenic acid to 1,3-diaminopropane molecule. The DAPS complex is stabilised by the presence of O-H···O and N-H···O hydrogen bonds and the electrostatic interactions as well. The N···O and O···O bond distances are 2.82-2.91 and 2.77 Å, respectively. The FT-IR and FT-Raman spectra of 1,3-diammonium propyl selenate monohydrate are recorded and the complete vibrational assignments have been discussed. The geometry is optimised by B3LYP method using 6-311G, 6-311+G and 6-311+G* basis sets and the energy, structural parameters, vibrational frequencies, IR and Raman intensities are determined. Differential scanning colorimetry (DSC) data were also presented to analyse the possibility of the phase transition. Complete natural bonding orbital (NBO) analysis is carried out to analyse the intramolecular electronic interactions and their stabilisation energies. The electrostatic potential of the complex lies in the range +1.902e × 10-2 to -1.902e × 10-2. The limits of total electron density of the complex is +8.43e × 10-2 to -8.43e × 10-2.

  5. FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin

    Science.gov (United States)

    Arjunan, V.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

    2013-05-01

    3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm-1, respectively. 1H and 13C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G**, high level 6-311++G** and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method.

  6. Self-Aggregation in Pyrrole:  Matrix Isolation, Solid State Infrared Spectroscopy, and DFT Study

    OpenAIRE

    Gómez-Zavaglia, Andrea; Fausto, Rui

    2004-01-01

    Pyrrole (C4H5N) was embedded in low-temperature solid inert matrixes (argon, xenon; T = 9 K) and both the monomer and low-order aggregates characterized by FTIR spectroscopy. The spectroscopic studies were complemented by extensive theoretical [DFT(B3LYP)/6-311++G(d,p)] structural and vibrational studies carried out for the monomer and their self-aggregates (up to four units). The calculated spectrum for monomeric pyrrole fits well those obtained immediately after deposition (at 9 K) of dilut...

  7. Structure-activity relations of 2-(methylthio)benzimidazole by FTIR, FT-Raman, NMR, DFT and conceptual DFT methods.

    Science.gov (United States)

    Arjunan, V; Raj, Arushma; Ravindran, P; Mohan, S

    2014-01-24

    The vibrational fundamental modes of 2-(methylthio)benzimidazole (2MTBI) have been analysed by combining FTIR, FT-Raman and quantum chemical calculations. The structural parameters of the compound are determined from the optimised geometry by B3LYP with 6-31G(∗∗), 6-311++G(∗∗) and cc-pVTZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities and Raman activities. (1)H and (13)C NMR spectra have been analysed and (1)H and (13)C nuclear magnetic resonance chemical shifts are calculated using the gauge independent atomic orbital (GIAO) method. The structure-activity relationship of the compound is also investigated by conceptual DFT methods. The chemical reactivity and site selectivity of the molecule has been determined with the help of global and local reactivity descriptors. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin.

    Science.gov (United States)

    Arjunan, V; Sakiladevi, S; Marchewka, M K; Mohan, S

    2013-05-15

    3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. (1)H and (13)C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. DFT molecular modeling and NMR conformational analysis of a new longipinenetriolone diester

    Science.gov (United States)

    Cerda-García-Rojas, Carlos M.; Guerra-Ramírez, Diana; Román-Marín, Luisa U.; Hernández-Hernández, Juan D.; Joseph-Nathan, Pedro

    2006-05-01

    The structure and conformational behavior of the new natural compound (4 R,5 S,7 S,8 R,9 S,10 R,11 R)-longipin-2-en-7,8,9-triol-1-one 7-angelate-9-isovalerate (1) isolated from Stevia eupatoria, were studied by molecular modeling and NMR spectroscopy. A Monte Carlo search followed by DFT calculations at the B3LYP/6-31G* level provided the theoretical conformations of the sesquiterpene framework, which were in full agreement with results derived from the 1H- 1H coupling constant analysis.

  10. DFT simulation, quantum chemical electronic structure, spectroscopic and structure-activity investigations of 2-benzothiazole acetonitrile.

    Science.gov (United States)

    Arjunan, V; Thillai Govindaraja, S; Jose, Sujin P; Mohan, S

    2014-07-15

    The Fourier transform infrared and FT-Raman spectra of 2-benzothiazole acetonitrile (BTAN) have been recorded in the range 4000-450 and 4000-100 cm(-1) respectively. The conformational analysis of the compound has been carried out to obtain the stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers derived theoretically by B3LYP gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The (1)H (400 MHz; CDCl3) and (13)C (100 MHz;CDCl3) nuclear magnetic resonance (NMR) spectra are also recorded. The electronic properties, the energies of the highest occupied and lowest unoccupied molecular orbitals are measured by DFT approach. The kinetic stability of the molecule has been determined from the frontier molecular orbital energy gap. The charges of the atoms and the structure-chemical reactivity relations of the compound are determined by its chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods. The non-linear optical properties of the compound have been discussed by measuring the polarisability and hyperpolarisability tensors. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Identification of a variant form of tyrosine phosphatase LYP

    Directory of Open Access Journals (Sweden)

    Ho Wanting T

    2010-11-01

    Full Text Available Abstract Background Protein tyrosine phosphatases (PTPs are important cell signaling regulators with major pathological implications. LYP (also known as PTPN22 is an intracellular enzyme initially found to be predominately expressed in lymphocytes. Importantly, an allelic R620W variant of LYP is strongly associated with multiple autoimmune diseases, including systemic lupus erythematosus, rheumatoid arthritis, type 1 diabetes, and autoimmune thyroid disease. Results In this study, we isolated a novel isoform of LYP designated LYP3. LYP3 differs from LYP1, the known isoform of LYP, in that it lacks a 28 amino acid segment right after the R620W site embedded in a proline-rich protein-protein interaction motif. Genomic sequence analysis revealed that LYP3 resulted from alternative splicing of the LYP gene located on chromosome 1p 13.3-13.1. Reverse transcription PCR analyses of 48 human tissues demonstrated that both LYP1 and LYP3 are predominantly expressed in primary and secondary lymphoid tissues but the relative expression levels of the two isoforms varies in different human tissues and individuals. Conclusions We thus identified a new variant form of LYP and conducted a comprehensive analysis of LYP tissue expressions. Considering the pathogenesis of LYP R620W, we believe that the expression of LYP3 may have an important role in regulating activity and function of LYP and may be implicated in autoimmune diseases.

  12. Prediction Errors of Molecular Machine Learning Models Lower than Hybrid DFT Error.

    Science.gov (United States)

    Faber, Felix A; Hutchison, Luke; Huang, Bing; Gilmer, Justin; Schoenholz, Samuel S; Dahl, George E; Vinyals, Oriol; Kearnes, Steven; Riley, Patrick F; von Lilienfeld, O Anatole

    2017-11-14

    evidence that ML model predictions deviate from DFT (B3LYP) less than DFT (B3LYP) deviates from experiment for all properties. Furthermore, out-of-sample prediction errors with respect to hybrid DFT reference are on par with, or close to, chemical accuracy. The results suggest that ML models could be more accurate than hybrid DFT if explicitly electron correlated quantum (or experimental) data were available.

  13. Synthesis, molecular structure, FT-IR and XRD investigations of 2-(4-chlorophenyl)-2-oxoethyl 2-chlorobenzoate: a comparative DFT study.

    Science.gov (United States)

    Chidan Kumar, C S; Fun, Hoong Kun; Tursun, Mahir; Ooi, Chin Wei; Chandraju, Siddegowda; Quah, Ching Kheng; Parlak, Cemal

    2014-04-24

    2-(4-Chlorophenyl)-2-oxoethyl 2-chlorobenzoate has been synthesized, its structural and vibrational properties have been reported using FT-IR and single-crystal X-ray diffraction (XRD) studies. The conformational analysis, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the synthesized compound (C15H10Cl2O3) have been examined by means of Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) method together with 6-31++G(d,p) basis set. Furthermore, reliable conformational investigation and vibrational assignments have been made by the potential energy surface (PES) and potential energy distribution (PED) analyses, respectively. Calculations are performed with two possible conformations. The title compound crystallizes in orthorhombic space group Pbca with the unit cell dimensions a=12.312(5) Å, b=8.103(3) Å, c=27.565(11) Å, V=2750.0(19) Å(3). B3LYP method provides satisfactory evidence for the prediction of vibrational wavenumbers and structural parameters. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. DFT Study of Optical Properties of Pt-based Complexes

    Science.gov (United States)

    Oprea, Corneliu I.; Dumbravǎ, Anca; Moscalu, Florin; Nicolaides, Atnanassios; Gîrţu, Mihai A.

    2010-01-01

    We report Density Functional Theory (DFT) calculations providing the geometrical and electronic structures, as well as the vibrational and optical properties of the homologous series of Pt-pyramidalized olefin complexes (CH2)n-(C8H10)Pt(PH3)2, where n = 0, 1, and 2, in their neutral and oxidized states. All complexes were geometry optimized for the singlet ground state in vacuum using DFT methods with B3LYP exchange-correlation functional and the Effective Core Potential LANL2DZ basis set, within the frame of Gaussian03 quantum chemistry package. We find the coordination geometry of Pt to be distorted square planar, with dihedral angles ranging from 0°, for n = 0 and 1, which have C2V symmetry to 3.4°, for n = 2 with C2 symmetry. The Mulliken charge analysis allows a discussion of the oxidation state of the Pt ion. Electronic transitions were calculated at the same level of theory by means of Time Dependant-DFT. For n = 2 the electronic absorption bands are located in the UV region of the spectrum, the transitions being assigned to metal to ligand charge transfers. The relevance of these Pt-based compounds as possible pigments for dye-sensitized solar cells is discussed.

  15. Predicting near-UV electronic circular dichroism in nucleosomal DNA by means of DFT response theory.

    Science.gov (United States)

    Norman, Patrick; Parello, Joseph; Polavarapu, Prasad L; Linares, Mathieu

    2015-09-14

    It is demonstrated that time-dependent density functional theory (DFT) calculations can accurately predict changes in near-UV electronic circular dichroism (ECD) spectra of DNA as the structure is altered from the linear (free) B-DNA form to the supercoiled N-DNA form found in nucleosome core particles. At the DFT/B3LYP level of theory, the ECD signal response is reduced by a factor of 6.7 in going from the B-DNA to the N-DNA form, and it is illustrated how more than 90% of the individual base-pair dimers contribute to this strong hypochromic effect. Of the several inter-base pair parameters, an increase in twist angles is identified as to strongly contribute to a reduced ellipticity. The present work provides first evidence that first-principles calculations can elucidate changes in DNA dichroism due to the supramolecular organization of the nucleoprotein particle and associates these changes with the local structural features of nucleosomal DNA.

  16. Determination of structural and spectroscopic parameters of 4-hydroxyantipyrine, using DFT method

    International Nuclear Information System (INIS)

    Catikkas, B.; Aktan, E.

    2010-01-01

    In this study, structural and vibrational parameters were calculated. First of all, conformational analysis of 4-hydroxyantipyrine was carried out in gas phase. Then, the geometric parameters (bond length, bond angle and tortion angle) of the most stable conformer were calculated and the Infrared and Raman frequencies of fundamental modes were determined. Calculations were made by using DFT B3LYP/6-311+G(d,p) method implemented the Gaussian 03 program. Afterwards, vibrational assignments of the title molecule were calculated by using Scaled Quantum Mechanical (SQM) analysis. In conclusion, calculated values were compared with corresponding experimental results.

  17. Parallel Implementation of Gamma-Point Pseudopotential Plane-Wave DFT with Exact Exchange

    International Nuclear Information System (INIS)

    Bylaska, Eric J.; Tsemekhman, Kiril L.; Baden, Scott B.; Weare, John H.; Jonsson, Hannes

    2011-01-01

    One of the more persistent failures of conventional density functional theory (DFT) methods has been their failure to yield localized charge states such as polarons, excitons and solitons in solid-state and extended systems. It has been suggested that conventional DFT functionals, which are not self-interaction free, tend to favor delocalized electronic states since self-interaction creates a Coulomb barrier to charge localization. Pragmatic approaches in which the exchange correlation functionals are augmented with small amount of exact exchange (hybrid-DFT, e.g. B3LYP and PBE0) have shown promise in localizing charge states and predicting accurate band gaps and reaction barriers. We have developed a parallel algorithm for implementing exact exchange into pseudopotential plane-wave density functional theory and we have implemented it in the NWChem program package. The technique developed can readily be employed in plane-wave DFT programs. Furthermore, atomic forces and stresses are straightforward to implement, making it applicable to both confined and extended systems, as well as to Car-Parrinello ab initio molecular dynamic simulations. This method has been applied to several systems for which conventional DFT methods do not work well, including calculations for band gaps in oxides and the electronic structure of a charge trapped state in the Fe(II) containing mica, annite.

  18. A combined experimental and computational study of 3-bromo-5-(2,5-difluorophenyl) pyridine and 3,5-bis(naphthalen-1-yl)pyridine: Insight into the synthesis, spectroscopic, single crystal XRD, electronic, nonlinear optical and biological properties

    Science.gov (United States)

    Ghiasuddin; Akram, Muhammad; Adeel, Muhammad; Khalid, Muhammad; Tahir, Muhammad Nawaz; Khan, Muhammad Usman; Asghar, Muhammad Adnan; Ullah, Malik Aman; Iqbal, Muhammad

    2018-05-01

    Carbon-carbon coupling play a vital role in the synthetic field of organic chemistry. Two novel pyridine derivatives: 3-bromo-5-(2,5-difluorophenyl)pyridine (1) and 3,5-bis(naphthalen-1-yl)pyridine (2) were synthesized via carbon-carbon coupling, characterized by XRD, spectroscopic techniques and also investigated by using density functional theory (DFT). XRD data and optimized DFT studies are found to be in good correspondence with each other. The UV-Vis analysis of compounds under study i.e. (1) and (2) was obtained by using "TD-DFT/B3LYP/6-311 + G(d,p)" level of theory to explain the vertical transitions. Calculated FT-IR and UV-Vis results are found to be in good agreement with experimental FT-IR and UV-Vis findings. Natural bond orbital (NBO) study was performed using B3LYP/6-311 + G(d,p) level to find the most stable molecular structure of the compounds. Frontier molecular orbital (FMO) analysis were performed at B3LYP/6-311 + G(d,p) level of theory, which indicates that the molecules might be bioactive. Moreover, the bioactivity of compounds (1) and (2) have been confirmed by the experimental activity in terms of zones of inhibition against bacteria and fungus. Chemical reactivity of compounds (1) and (2) was indicated by mapping molecular electrostatic potential (MEP) over the entire stabilized geometries of the compounds under study. The nonlinear optical properties were computed with B3LYP/6-311 + G(d,p) level of theory which are found greater than the value of urea due to conjugation effect. Two state model has been further employed to explain the nonlinear optical properties of compounds under investigation.

  19. Multi-Paradigm Multi-Scale Simulations for Fuel Cell Catalysts and Membranes

    Science.gov (United States)

    2006-01-01

    transfer studies on model systems. . Applying newly developed density functionals QM ( X3LYP ) for estimating the thermodynamics and kinetic energy...Density functional theory methods We have used many QM methods to probe chemical reaction mechanisms and find that the B3LYP and X3LYP [6] flavors of DFT...carried out QM calculations on the surface reactivity of the Pt and PtRu anode catalysts. This QM uses a new ab initio DFT-GGA method ( X3LYP ) [6

  20. Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg; Kjærgaard, Henrik Grum

    2015-01-01

    The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHand...

  1. Understanding the HIV-1 protease reactivity with DFT: what do we gain from recent functionals?

    Science.gov (United States)

    Garrec, J; Sautet, P; Fleurat-Lessard, P

    2011-07-07

    The modeling of HIV-1 plays a crucial role in the understanding of its reactivity and its interactions with specific drugs. In this work, we propose a medium sized model to test the ability of a variety of quantum chemistry approaches to provide reasonable geometric parameters and energetics for this system. Although our model is large enough to include the main polarizing groups of the active site, it is small enough to be used within full quantum studies up to the second order Møller-Plesset (MP2) level with extrapolations to coupled cluster CCSD(T) level. These high level calculations are used as reference to assess the ability of electronic structure methods (semiempirical and DFT) to provide accurate geometries and energies for the HIV-1 protease reaction. All semiempirical methods fail to describe the geometry of the protease active site. Within DFT, pure generalized gradient approximation (GGA) functionals have difficulty in reproducing the reaction energy and underestimate the barrier. Hybrid and/or meta GGA approaches do not yield a consistent improvement. The best results are obtained with hybrid GGA B3LYP or X3LYP and with hybrid meta GGA functionals with a fraction of exact exchange around 30-40%, such as M06, B1B95, or BMK functionals. On the basis of these results, we propose an accurate and computationally efficient strategy, employing quantum chemistry methods. This is applied here to study the protonation state of the reaction intermediate and could be easily used in further QM/MM studies.

  2. Molecular Disorder in (‒-Encecanescin

    Directory of Open Access Journals (Sweden)

    Benito Reyes-Trejo

    2014-04-01

    Full Text Available (‒-Encecanescin (1 has been isolated from the leaves of Eupatorium aschembornianum. Two conformers are present in the crystal structure as a result of molecular disorder. The structure of 1 was established by 1H- and 13C-NMR spectroscopy in CDCl3 solution using 2D NMR techniques (gHSQC, gHMBC and NOESY. A Monte Carlo random search using molecular mechanics followed by the geometry optimization of each minimum energy structure using density functional theory (DFT calculations at the B3LYP/6–31G* level and a Boltzmann analysis of the total energies generated accurate molecular models describing the conformational behavior of 1. The three most stable conformers 2–4 of compound 1 were reoptimized at the B3LYP/6-311++G(d,p level of theory using CHCl3 as a solvent. Correlations between the experimental 1H- and 13C-NMR chemical shifts (δexp have been found, and the GIAO/B3LYP/6-311++G(d,p calculated magnetic isotropic shielding tensors (σcalc for conformers 2 and 3, δexp = a + b σcalc, are reported. A good linear relationship between the experimental and calculated NMR data has been obtained for protons and carbon atoms.

  3. Studies on the self-catalyzed Knoevenagel condensation, characterization, DPPH radical scavenging activity, cytotoxicity, and molecular properties of 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones using single crystal XRD and DFT techniques

    Science.gov (United States)

    Suresh Kumar, G. S.; Antony Muthu Prabhu, A.; Bhuvanesh, N.

    2014-10-01

    We have studied the self-catalyzed Knoevenagel condensation, spectral characterization, DPPH radical scavenging activity, cytotoxicity, and molecular properties of 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones using single crystal XRD and DFT techniques. In the absence of any catalyst, a series of novel 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones were synthesized using Meldrum’s acid and formylphenoxyaliphatic acid(s) in water. These molecules are arranged in the dimer form through intermolecular H-bonding in the single crystal XRD structure. Compounds have better DPPH radical scavenging activity and cytotoxicity against A431 cancer cell line. The optimized molecular structure, natural bond orbital analysis, electrostatic potential map, HOMO-LUMO energies, molecular properties, and atomic charges of these molecules have been studied by performing DFT/B3LYP/3-21G(*) level of theory in gas phase.

  4. Structural, vibrational spectroscopic and nonlinear optical activity studies on 2-hydroxy- 3, 5-dinitropyridine: A DFT approach

    Science.gov (United States)

    Asath, R. Mohamed; Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

    2015-06-01

    The conformational analysis was carried out for 2-Hydroxy- 3, 5-dinitropyridine molecule using potential energy surface scan and the most stable optimized conformer was predicted. The vibrational frequencies and Mulliken atomic charge distribution were calculated for the optimized geometry of the molecule using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intramolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness values of the title molecule were carried out. The nonlinear optical activity of the molecule was studied by means of first order hyperpolarizability, which was computed as 7.64 times greater than urea. The natural bond orbital analysis was performed to confirm the nonlinear optical activity of the molecule.

  5. Synthesis, FTIR, FT-Raman, UV-visible, ab initio and DFT studies on benzohydrazide.

    Science.gov (United States)

    Arjunan, V; Rani, T; Mythili, C V; Mohan, S

    2011-08-01

    A systematic vibrational spectroscopic assignment and analysis of benzohydrazide (BH) has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis were aided by electronic structure calculations--ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) performed with 6-31G(d,p) and 6-311++G(d,p) basis sets. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λ(max) were determined by time-dependent DFT (TD-DFT) method. The geometrical, thermodynamical parameters and absorption wavelengths were compared with the experimental data. The interactions of carbonyl and hydrazide groups on the benzene ring skeletal modes were investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. HYDROGEN MOLECULE INTERACTION WITH CpCr(CO3 CATALYST

    Directory of Open Access Journals (Sweden)

    T. Spataru

    2013-12-01

    Full Text Available The hydrogen molecule interaction with CpCr (CO3 catalyst has been studied using the B3LYP, B86 functionals and the 6-311++G** , LACV3P basis sets. The best results in the testing calculations of the analyzed reaction have been obtained by using the B86/6-311++G** DFT version giving quite good agreement between experimental and theoretical calculated enthalpies. The dispersion corrected DFT Grimme’s and Head-Gordon and coworkers’functionals have been attempted without any improvement of the results. The free energies of the initial reactants, transition states, intermediate compounds and fi nal products of the typical six-ring bond modifi cation mechanism have been calculated. The energy barriersof the reaction pathways are too high in the DFT approximation.

  7. Spectroscopic and density functional theory studies of trans-3-(trans-4-imidazolyl)acrylic acid.

    Science.gov (United States)

    Arjunan, V; Remya, P; Sathish, U; Rani, T; Mohan, S

    2014-08-14

    The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry of trans-3-(trans-4-imidazolyl)acrylic acid have been determined from B3LYP methods with 6-311++G(**) and cc-pVTZ basis sets. The effects of substituents (acrylyl group) on the imidazole vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of trans-3-(trans-4-imidazolyl)acrylic acid have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. (1)H and (13)C NMR isotropic chemical shifts are calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound are also determined from DFT method. The total electron density and electrostatic potential of the compound are determined by natural bond orbital analysis. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities employing natural population analysis (NPA) are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Quantum mechanical study and spectroscopic (FT-IR, FT-Raman, UV-Visible) study, potential energy surface scan, Fukui function analysis and HOMO-LUMO analysis of 3-tert-butyl-4-methoxyphenol by DFT methods.

    Science.gov (United States)

    Saravanan, S; Balachandran, V

    2014-09-15

    This study represents an integral approach towards understanding the electronic and structural aspects of 3-tert-butyl-4-methoxyphenol (TBMP). Fourier-transform Infrared (FT-IR) and Fourier-transform Raman (FT-Raman) spectra of TBMP was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) methods using 6-311++G (d,p) basis set. The most stable conformer of TBMP was identified from the computational results. The assignments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of TBMP have been discussed. The stability and charge delocalization of the molecule was studied by Natural Bond Orbital (NBO) analysis. UV-Visible spectrum and effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach with B3LYP/6-311++G (d,p) level of theory. The molecule orbital contributions are studied by density of energy states (DOSs). The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MEP). Mulliken analysis of atomic charges is also calculated. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacities, standard entropy and standard enthalpy changes with temperatures. Global hardness, global softness, global electrophilicity and ionization potential of the title compound are determined. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

    Science.gov (United States)

    Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

    2018-06-01

    Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.

  10. Relative Stability of the La and Lb Excited States in Adenine and Guanine: Direct Evidence from TD-DFT Calculations of MCD Spectra.

    Science.gov (United States)

    Santoro, Fabrizio; Improta, Roberto; Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick; Coriani, Sonia

    2014-06-05

    The relative position of La and Lb ππ* electronic states in purine nucleobases is a much debated topic, since it can strongly affect our understanding of their photoexcited dynamics. To assess this point, we calculated the absorption and magnetic circular dichroism (MCD) spectra of adenine, guanine, and their nucleosides in gas-phase and aqueous solution, exploiting recent developments in MCD computational technology within time-dependent density functional theory. MCD spectroscopy allows us to resolve the intense S0→ La transition from the weak S0→ Lb transition. The spectra obtained in water solution, by using B3LYP and CAM-B3LYP functionals and describing solvent effect by cluster models and by the polarizable continuum model (PCM), are in very good agreement with the experimental counterparts, thus providing direct and unambiguous evidence that the energy ordering predicted by TD-DFT, La < Lb, is the correct one.

  11. Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional

    OpenAIRE

    Su, Julius T.; Xu, Xin; Goddard, William A., III

    2004-01-01

    We predict structures and energies of water clusters containing up to 19 waters with X3LYP, an extended hybrid density functional designed to describe noncovalently bound systems as accurately as covalent systems. Our work establishes X3LYP as the most practical ab initio method today for calculating accurate water cluster structures and energies. We compare X3LYP/aug-cc-pVTZ energies to the most accurate theoretical values available (n = 2−6, 8), MP2 with basis set superposition error (BSSE)...

  12. DFT Study of Electronic and Optical Properties of Small Oligothiophenes Based on Terthiophene End-capped by Several Donor Groups

    Directory of Open Access Journals (Sweden)

    El Alamy Aziz

    2017-07-01

    Full Text Available Eight small molecules based on terthiophene end-capped by several donor groups have been carried out using density functional theory (DFT and time-dependent (TDDFT methods in neutral and doped states. The theoretical ground-state geometry, electronic structure and optical properties of the studied molecules were obtained by the DFT and TD-DFT methods at the B3LYP level with 6-31G(d basis set. Theoretical knowledge of the highest occupied molecular orbital (HOMO, the lowest unoccupied molecular orbital (LUMO energy levels the gap energy (Eg and the open-circuit voltage (Voc of the studied compounds are calculated and discussed. The effects of the donor group substituents on the geometries and optoelectronic properties of these materials are discussed to investigate the relationship between molecular structure and optoelectronic properties. The results of this work suggest some of these materials as a good candidate for organic solar cells. DOI: http://dx.doi.org/10.17807/orbital.v9i3.995

  13. Vibrational spectroscopic, structural and nonlinear optical activity studies on 2-amino-3-chloro-5-trifluoromethyl pyridine: A DFT approach

    Science.gov (United States)

    Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

    2016-05-01

    The conformational analysis was carried out for 2-amino-3-chloro-5-trifluoromethylpyridine using potential energy surface (PES) scan and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program package. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness of the molecule were carried out. The nonlinear optical (NLO) activity was studied and the first order hyperpolarizability value was computed, which was 3.48 times greater than the urea. The natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ACTP molecule is a promising candidate for NLO materials.

  14. Rate constants of hydroxyl radical oxidation of polychlorinated biphenyls in the gas phase: A single−descriptor based QSAR and DFT study

    International Nuclear Information System (INIS)

    Yang, Zhihui; Luo, Shuang; Wei, Zongsu; Ye, Tiantian; Spinney, Richard; Chen, Dong; Xiao, Ruiyang

    2016-01-01

    The second‒order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure–activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi−linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = −0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas‒phase ·OH oxidation of 2,4′,5-trichlorobiphenyl (PCB31), 2,2′,4,4′-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB169), and 2,3,3′,4,5,5′,6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6–311++G**//B3LYP/6–31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single–descriptor based QSAR model we developed. - Highlights: • We developed a single−descriptor based QSAR model for ·OH oxidation of PCBs. • We independently validated the QSAR predicted k values of five PCB congeners with the DFT method. • The QSAR predicted and DFT calculated k for the five PCB congeners exhibit excellent agreement. - We developed a single

  15. Synthesis, spectroscopic, DFT calculations and biological activity studies of ruthenium carbonyl complexes with 2-picolinic acid and a secondary ligand

    Science.gov (United States)

    Shohayeb, Shahera M.; Mohamed, Rania G.; Moustafa, H.; El-Medani, Samir M.

    2016-09-01

    Thermal reaction of [Ru3(CO)12] with 2-picolinic acid (Hpic) in the absence and presence of a secondary ligand (pyridine, Py, bipyridine, Bipy, or thiourea, Tu) was investigated. Four complexes with molecular formulae: [Ru(CO)3(Hpic)], 1, [Ru2(CO)5(Hpic)(Py)], 2, [Ru2(CO)5(Hpic)(Tu)], 3 and [Ru2(CO)4(Hpic)(Bipy)], 4, were isolated. All complexes were characterized based on elemental analyses, IR, 1H NMR, magnetic studies, mass spectrometry and thermal analysis. The ligand and its complexes have been screened for antibacterial activities. Density Functional Theory (DFT) calculations at the B3LYP/6-311G (d,p)_ level of theory have been carried out to investigate the equilibrium geometry of the ligands. The optimized geometry parameters of the complexes were evaluated using B3LYP method and LANL2DZ basis set. The extent of natural charge population (core, valence and rydberg), exact electronic configuration, total Lewis and total non-Lewis are estimated and discussed in terms of natural bond orbitals (NBO) analysis.

  16. Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions.

    Science.gov (United States)

    Yamada, Michio; Slanina, Zdenek; Mizorogi, Naomi; Muranaka, Atsuya; Maeda, Yutaka; Nagase, Shigeru; Akasaka, Takeshi; Kobayashi, Nagao

    2013-03-14

    We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C(2v)-C(82), La(2)@I(h)-C(80), and Sc(3)N@I(h)-C(80) can be assigned using these techniques. Particularly, a difference in the electronic transitions between La(2)@I(h)-C(80) and Sc(3)N@I(h)-C(80), which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La(2)@I(h)-C(80) were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La(2)@I(h)-C(80), although no marked difference exists in their absorption spectra.

  17. Vibrational, electronic and quantum chemical studies of 1,2,4-benzenetricarboxylic-1,2-anhydride.

    Science.gov (United States)

    Arjunan, V; Raj, Arushma; Subramanian, S; Mohan, S

    2013-06-01

    The FTIR and FT-Raman spectra of 1,2,4-benzenetricarboxylic-1,2-anhydride (BTCA) have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The complete vibrational assignments and analysis of BTCA have been performed. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP, MP2, B3PW91) method using 6-311++G(**), 6-31G(**) and cc-pVTZ basis sets. The structural parameters, energies, thermodynamic parameters, vibrational frequencies and the NBO charges of BTCA were determined by the DFT method. The (1)H and (13)C isotropic chemical shifts (δ ppm) of BTCA with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. The delocalization energies of different types of interactions were determined. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. DIPYRIDOXYL(1,8-DIAMINO-3,6-DIOXAOCTANE) SCHIFF-BASE

    African Journals Online (AJOL)

    Preferred Customer

    KEY WORDS: Schiff base, N,N′-dipyridoxyl(1,8-diamino-3,6-dioxaoctane), DFT, B3LYP. INTRODUCTION. Schiff bases due to structural varieties and unique characteristics are the most versatile studied ligands in coordination chemistry [1, 2] and their metal complexes play an important role in the development of inorganic ...

  19. Favorable performance of the DFT methods in predicting the minimum-energy structure of the lowest triplet state of WF4

    International Nuclear Information System (INIS)

    Gutowski, M.; Univ. of Utah, Salt Lake City, UT

    1999-01-01

    The tetrahedral structure of the lowest triplet state of the WF 4 complex was examined using different variants of the density functional theory (DFT) and conventional ab initio methods. The low-level, conventional, ab initio methods, such as SCF, MP2, MP3, and CISD, predict the tetrahedral structure to be a minimum, whereas the DFT schemes predict an imaginary frequency for the e vibrational mode. Only after recovering electron correlation effects at the MP4 and higher levels, the conventional electronic structure methods also predict the T d structure to be a second-order stationary point. This is not the correlation but the exchange part of the DFT functionals which is responsible for the discrepancy between the DFT and low-level, conventional, ab initio predictions. The lowering of symmetry to C 2v leads to a minimum on the lowest triplet potential energy surface and the electronic energy difference between the T d and C 2v stationary points amounts to 0.85 and 0.96 kcal/mol at the B3LYP and CCSD(T) levels, respectively

  20. Synthesis, Characterisation and DFT Calculations of Azo-Imine Dyes

    Directory of Open Access Journals (Sweden)

    Sevil Özkınalı

    2017-11-01

    Full Text Available In this study, azo dyes containing an imine group were synthesised by coupling p-hydroxybenzylidene aniline with the diazonium salts of p-toluidine, 4-aminophenol, aniline, p-chloroaniline, p-fluoroaniline, and p-nitroaniline. The compounds were characterised by melting point, elemental, UV-Vis and IR analyses as well as 1H-NMR and 13C-NMR spectroscopies. Moreover, the experimental data were supplemented with density functional theory (DFT calculations. The experimental data on FT-IR and UV–Vis spectra of the compounds were compared with theoretical results. The DFT calculations were performed to obtain the ground state geometries of the compounds using the B3LYP hybrid functional level with 6-311++g(2d,2p basis set. Frontier molecular orbital energies, band gap energies and some chemical reactivity parameters, such as chemical hardness and electronegativity, were calculated and compared with experimental values. A significant correlation was observed between the dipole moment and polarities of the solvents and the absorption wavelength of the compounds.

  1. The vibrational structure of (E,E’)-1,4-diphenyl-1,3-butadiene. Linear dichroism FTIR spectroscopy and quantum chemical calculations

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Møller, Søren; Spanget-Larsen, Jens

    2006-01-01

    than 40 vibrational transitions. The observed IR wavenumbers, relative intensities, and polarization directions were generally well reproduced by the results of a harmonic analysis based on B3LYP/cc-pVTZ density functional theory (DFT). The combined experimental and theoretical results led to proposal...... of a nearly complete assignment of the IR active fundamentals of DPB, involving reassignment of a number of transitions. In addition, previously published Raman spectra of DPB were well predicted by the B3LYP/cc-pVTZ calculations....

  2. Spectroscopy, crystal structure, valance molecular orbital energy level diagram and DFT study of cis-[Cr(2,2'-bipy) 2Cl 2](Cl) 0.38(PF 6) 0.62

    Science.gov (United States)

    Kar, Tapas; Liao, Meng-Sheng; Biswas, Susobhan; Sarkar, Saikat; Dey, Kamalendu; Yap, Glenn P. A.; Kreisel, Kevin

    2006-11-01

    A new octahedral chromium(III) complex having 2,2'-bipyridine as ligand system was synthesized in methanol. Single crystal X-ray diffraction analysis shows that it possesses non-stoichiometry in its anionic primary covalency. It has also been studied by elemental analyses, optical spectroscopy (UV-vis, IR) and magnetic susceptibility data. DFT calculations (with B3LYP functional and double-ξ quality LANLDZ(D95V) basis set) were carried out to interpret the electronic and infrared spectra of the complex. The DFT optimized geometric structure for the complex is compared with the X-ray crystallographic data; the theory-experiment agreement is satisfactory.

  3. Crystal structure, vibrational spectra and DFT studies of hydrogen bonded 1,2,4-triazolium hydrogenselenate

    Science.gov (United States)

    Arjunan, V.; Thirunarayanan, S.; Marchewka, M. K.; Mohan, S.

    2017-10-01

    The new hydrogen bonded molecular complex 1,2,4-triazolium hydrogenselenate (THS) is prepared by the reaction of 1H-1,2,4-triazole and selenic acid. This complex is stabilised by N-H⋯O and C-H⋯O hydrogen bonding and electrostatic attractive forces between 1H and 1,2,4-triazolium cations and hydrogen selenate anions. The XRD studies revealed that intermolecular proton transfer occur from selenic acid to 1H-1,2,4-triazole molecule, results in the formation of 1,2,4-triazolium hydrogenselenate which contains 1,2,4-triazolium cations and hydrogenselenate anions. The molecular structure of THS crystal has also been optimised by using Density Functional Theory (DFT) using B3LYP/cc-pVTZ and B3LYP/6-311++G** methods in order to find the whole characteristics of the molecular complex. The theoretical structural parameters such as bond length, bond angle and dihedral angle determined by DFT methods are well agreed with the XRD parameters. The atomic charges and thermodynamic properties are also calculated and analysed. The energies of frontier molecular orbitals HOMO, LUMO, HOMO-1, LUMO+1 and LUMO-HUMO energy gap are calculated to understand the kinetic stability and chemical reactivity of the molecular complex. The natural bond orbital analysis (NBO) has been performed in order to study the intramolecular bonding interactions and delocalisation of electrons. These intra molecular charge transfer may induce biological activities such as antimicrobials, antiinflammatory, antifungal etc. The complete vibrational assignments of THS have been performed by using FT-IR and FT-Raman spectra.

  4. An accurate cost effective DFT approach to study the sensing behaviour of polypyrrole towards nitrate ions in gas and aqueous phases.

    Science.gov (United States)

    Wasim, Fatima; Mahmood, Tariq; Ayub, Khurshid

    2016-07-28

    Density functional theory (DFT) calculations have been performed to study the response of polypyrrole towards nitrate ions in gas and aqueous phases. First, an accurate estimate of interaction energies is obtained by methods calibrated against the gold standard CCSD(T) method. Then, a number of low cost DFT methods are also evaluated for their ability to accurately estimate the binding energies of polymer-nitrate complexes. The low cost methods evaluated here include dispersion corrected potential (DCP), Grimme's D3 correction, counterpoise correction of the B3LYP method, and Minnesota functionals (M05-2X). The interaction energies calculated using the counterpoise (CP) correction and DCP methods at the B3LYP level are in better agreement with the interaction energies calculated using the calibrated methods. The interaction energies of an infinite polymer (polypyrrole) with nitrate ions are calculated by a variety of low cost methods in order to find the associated errors. The electronic and spectroscopic properties of polypyrrole oligomers nPy (where n = 1-9) and nPy-NO3(-) complexes are calculated, and then extrapolated for an infinite polymer through a second degree polynomial fit. Charge analysis, frontier molecular orbital (FMO) analysis and density of state studies also reveal the sensing ability of polypyrrole towards nitrate ions. Interaction energies, charge analysis and density of states analyses illustrate that the response of polypyrrole towards nitrate ions is considerably reduced in the aqueous medium (compared to the gas phase).

  5. Coordination Behavior of Ni2+, Cu2+, and Zn2+ in Tetrahedral 1-Methylimidazole Complexes: A DFT/CSD Study

    OpenAIRE

    Tetteh, Samuel

    2018-01-01

    The interaction between nickel (Ni2+), copper (Cu2+), and zinc (Zn2+) ions and 1-methylimidazole has been studied by exploring the geometries of eleven crystal structures in the Cambridge Structural Database (CSD). The coordination behavior of the respective ions was further investigated by means of density functional theory (DFT) methods. The gas-phase complexes were fully optimized using B3LYP/GENECP functionals with 6-31G∗ and LANL2DZ basis sets. The Ni2+ and Cu2+ complexes show distorted ...

  6. Biomarkers of cigarette smoking and DNA methylating agents: Raman, SERS and DFT study of 3-methyladenine and 7-methyladenine

    Science.gov (United States)

    Harroun, Scott G.; Zhang, Yaoting; Chen, Tzu-Heng; Ku, Ching-Rong; Chang, Huan-Tsung

    2017-04-01

    3-Methyladenine and 7-methyladenine are biomarkers of DNA damage from exposure to methylating agents. For example, the concentration of 3-methyladenine increases significantly in the urine of cigarette smokers. Surface-enhanced Raman spectroscopy (SERS) has shown much potential for detection of biomolecules, including DNA. Much work has been dedicated to the canonical nucleobases, with comparatively fewer investigations of modified DNA and modified DNA nucleobases. Herein, Raman spectroscopy and SERS are used to examine the adsorption orientations of 3-methyladenine and 7-methyladenine on Ag nanoparticles. Density functional theory (DFT) calculations at the B3LYP level are used to support the conclusions via simulated spectra of the nucleobases and of Ag+/nucleobase complexes. The results herein show that 7-methyladenine adsorbs upright via its N3 and N9 atoms side, similarly to adenine. 3-Methyladenine adsorbs in a very tilted or flat orientation on the Ag nanoparticles. These findings will be useful for future SERS or other nanoparticle-based bioanalytical assays for detection of these methyladenines or other modified nucleobases.

  7. Synthesis of 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3, 5-dioxohepta-1, 6-dienyl)-2-methoxyphenyl 4-fluorobenzoate, a novel monoester derivative of curcumin, its experimental and theoretical (DFT) studies

    Science.gov (United States)

    Srivastava, Sangeeta; Gupta, Preeti; Amandeep; Singh, Ranvijay Pratap

    2016-04-01

    Curcumin (1), isolated as a major component from the chloroform extract of Curcuma longa was converted to its ester derivative 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dienyl)-2-methoxyphenyl 4-fluorobenzoate (2). The compound has been characterized with the help of 1H, 13C NMR, UV, IR and mass spectrometry. The molecular geometry of synthesized compound was calculated in ground state by Density functional theory (DFT/B3LYP) using 6-31G (d,p) basis set. 1H and 13C NMR chemical shifts were calculated in ground state by using Gauge-Including Atomic Orbital (GIAO) approach and these values were correlated with experimental observations. The electronic properties such as HOMO and LUMO energies were calculated using time dependent Density Functional Theory (TD-DFT). Stability of the molecule as a result of hyper conjugative interactions and electron delocalization were analysed using Natural bond orbital (NBO) analysis. Intramolecular interactions were analysed by AIM (Atom in molecule) approach. Global reactivity descriptors were calculated to study the reactive site within molecule. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out.

  8. DFT studies on the multi-channel reaction of CH3S+NO2

    Science.gov (United States)

    Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

    The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero-point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6-311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO.

  9. Evaluation of exchange-correlation functionals for time-dependent density functional theory calculations on metal complexes.

    Science.gov (United States)

    Holland, Jason P; Green, Jennifer C

    2010-04-15

    The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) 0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes. 2009 Wiley Periodicals, Inc.

  10. Influence of Exchange-Correlation Functional in the Calculations of Vertical Excitation Energies of Halogenated Copper Phthalocyanines using Time-Dependent Density Functional Theory (TD-DFT)

    International Nuclear Information System (INIS)

    Lee, Sang Uck

    2013-01-01

    The accurate prediction of vertical excitation energies is very important for the development of new materials in the dye and pigment industry. A time-dependent density functional theory (TD-DFT) approach coupled with 22 different exchange-correlation functionals was used for the prediction of vertical excitation energies in the halogenated copper phthalocyanine molecules in order to find the most appropriate functional and to determine the accuracy of the prediction of the absorption wavelength and observed spectral shifts. Among the tested functional, B3LYP functional provides much more accurate vertical excitation energies and UV-vis spectra. Our results clearly provide a benchmark calibration of the TD-DFT method for phthalocyanine based dyes and pigments used in industry

  11. Vibrational Spectroscopy Investigation Using Ab Initio and Density Functional Theory Analysis on the Structure of tert-Butyl 3a-Chloroperhydro-2,6a-epoxyoxireno[e]isoindole-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Hakan Arslan

    2013-01-01

    Full Text Available The molecular structure, vibrational frequencies, and infrared intensities of the tert-butyl 3a-chloroperhydro-2,6a-epoxyoxireno[e]isoindole-5-carboxylate were calculated by the HF and DFT (BLYP and B3LYP methods using 6-31G(d and 6-31G(d,p basis sets. The FT infrared spectrum of the solid sample was measured under standard condition. We obtained two stable conformers for the title compound; however Conformer 1 is approximately 0.2 kcal/mol more stable than the Conformer 2. The comparison of the theoretical and experimental geometry of the title compound shows that the X-ray parameters fairly well reproduce the geometry of Conformer 2. Comparison of the observed fundamental vibrational frequencies of the title molecule and calculated results by HF and DFT methods indicates that B3LYP is superior for molecular vibrational problems. The harmonic vibrations computed by the B3LYP/6-31G(d,p method are in a good agreement with the observed IR spectral data. Theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions (PEDs using VEDA 4 program.

  12. Synthesis, Crystal Structure, DFT Study and Antifungal Activity of 4-(5-((4-Bromobenzyl thio-4-Phenyl-4H-1,2,4-Triazol-3-ylpyridine

    Directory of Open Access Journals (Sweden)

    Jin-Xia Mu

    2015-12-01

    Full Text Available The title compound 4-(5-((4-bromobenzylthio-4-phenyl-4H-1,2,4-triazol-3-ylpyridine (C20H15BrN4S was synthesized, and its structure was confirmed by 1H NMR, MS and elemental analyses and single-crystal X-ray structure determination. It crystallizes in the triclinic space group P-1 with a = 7.717(3, b = 9.210(3, c = 13.370(5 Å, α = 80.347(13, β = 77.471(13, γ = 89.899(16°, V = 913.9(6 Å3, Z = 2 and R = 0.0260 for 3145 observed reflections with I > 2σ(I. A Density functional theory (DFT (B3LYP/6-31G calculation of the title molecule was carried out. The full geometry optimization was carried out using a 6-31G basis set, and the frontier orbital energy. Atomic net charges are discussed. Calculated bond lengths and bond angles were found to differ from experimental values, and the compound exhibits moderate antifungal activity.

  13. Comparison of the performance of different DFT methods in the calculations of the molecular structure and vibration spectra of serotonin (5-hydroxytryptamine, 5-HT)

    Science.gov (United States)

    Yang, Yue; Gao, Hongwei

    2012-04-01

    Serotonin (5-hydroxytryptamine, 5-HT) is a monoamine neurotransmitter which plays an important role in treating acute or clinical stress. The comparative performance of different density functional theory (DFT) methods at various basis sets in predicting the molecular structure and vibration spectra of serotonin was reported. The calculation results of different methods including mPW1PW91, HCTH, SVWN, PBEPBE, B3PW91 and B3LYP with various basis sets including LANL2DZ, SDD, LANL2MB, 6-31G, 6-311++G and 6-311+G* were compared with the experimental data. It is remarkable that the SVWN/6-311++G and SVWN/6-311+G* levels afford the best quality to predict the structure of serotonin. The results also indicate that PBEPBE/LANL2DZ level show better performance in the vibration spectra prediction of serotonin than other DFT methods.

  14. Charge-resonance excitations in symmetric molecules - Comparison of linear response DFT with CC3 for the excited states of a model dimer

    DEFF Research Database (Denmark)

    Kuhlman, Thomas Scheby; Mikkelsen, Kurt V.; Møller, Klaus Braagaard

    2009-01-01

    to a reference CC3 calculation revealing a better description of the excited states by CAM-B3LYP than that of B3LYP. The Λ parameter introduced by Peach et al. [M.J.G. Peach, P. Benfield, T. Helgaker, D.J. Tozer, J. Chem. Phys. 128 (2008) 044118] does not always reveal the problematic charge-resonance states...

  15. Synthesis, characterization, crystal structures and DFT studies of some new 1,2,4-triazole and triazolidin derivatives

    Science.gov (United States)

    Abosadiya, Hamza M.; Anouar, El Hassane; Abusaadiya, Salima M.; Hasbullah, Siti Aishah; Yamin, Bohari M.

    2018-01-01

    A simple efficient method for synthesis of some new 1,2,4-Triazole and Triazolidin derivatives namely, 5-(4-methoxyphenyl)-2-phenyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (1a), (2-chlorophenyl)(3,3-dimethyl-1-phenyl-5-thioxo-1,2,4-triazolidin-4-yl)methanone (1b) and (2-iodophenyl)(3,3-dimethyl-1-phenyl-5-thioxo-1,2,4-triazolidin-4-yl)methanone (1c) have been synthesized in high yields from the reaction of carbonoyl isothiocyanate with phenyl hydrazine. The final products were characterized by FT-IR, 1H and 13C NMR spectroscopic techniques. X-ray crystallographic studies showed that 1a crystallized in triclinic crystal system with space group Pī, while both 1b and 1c crystallized in orthorhombic crystal system with space group Pna21. The asymmetric unit of 1a consists two crystallographically independent molecules, while only one molecule in asymmetric unit for both 1b and 1c compounds. All molecules possess Csbnd H ….S intramolecular hydrogen bonds which formed a pseudo-six-membered ring. Experimental results have been confirmed by the state-of-art density functional theory (DFT) in gas and solvent phase by using five different hybrid functionals B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0 combined with 6-311++G(d, p) basis set. The experimental data are relatively well produced, and relatively good correlations are obtained between the predicted and experimental data.

  16. Infrared and Raman Spectra of and Isotopomers: A DFT-PT2 Anharmonic Study

    Directory of Open Access Journals (Sweden)

    Andrea Alparone

    2013-01-01

    Full Text Available IR and Raman spectra of selenophene and of its perdeuterated isotopomer have been obtained in gas phase through density-functional theory (DFT computations. Vibrational wavenumbers have been calculated using harmonic and anharmonic second-order perturbation theory (PT2 procedures with the B3LYP method and the 6-311 basis set. Anharmonic overtones have been determined by means of the PT2 method. The introduction of anharmonic terms decreases the harmonic wavenumbers, giving a significantly better agreement with the experimental data. The most significant anharmonic effects occur for the C–H and C–D stretching modes, the observed H/D isotopic wavenumber redshifts being satisfactorily reproduced by the PT2 computations within 6–20 cm−1 (1–3%. In the spectral region between 500 cm−1 and 1500 cm−1, the IR spectra are dominated by the out-of-plane C–H (C–D bending transition, whereas the Raman spectra are mainly characterized by a strong peak mainly attributed to the C=C + C–C bonds stretching vibration with the contribution of the in-plane C–H (C–D bending deformation. The current results confirm that the PT2 approach combined with the B3LYP/6-311 level of calculation is a satisfactory choice for predicting vibrational spectra of cyclic molecules.

  17. The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

    Science.gov (United States)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

    2017-10-01

    Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  18. Optical Absorption Spectra and Electronic Properties of Symmetric and Asymmetric Squaraine Dyes for Use in DSSC Solar Cells: DFT and TD-DFT Studies

    Directory of Open Access Journals (Sweden)

    Reda M. El-Shishtawy

    2016-04-01

    Full Text Available The electronic absorption spectra, ground-state geometries and electronic structures of symmetric and asymmetric squaraine dyes (SQD1–SQD4 were investigated using density functional theory (DFT and time-dependent (TD-DFT density functional theory at the B3LYP/6-311++G** level. The calculated ground-state geometries reveal pronounced conjugation in these dyes. Long-range corrected time dependent density functionals Perdew, Burke and Ernzerhof (PBE, PBE1PBE (PBE0, and the exchange functional of Tao, Perdew, Staroverov, and Scuseria (TPSSh with 6-311++G** basis set were employed to examine optical absorption properties. In an extensive comparison between the optical data and DFT benchmark calculations, the BEP functional with 6-311++G** basis set was found to be the most appropriate in describing the electronic absorption spectra. The calculated energy values of lowest unoccupied molecular orbitals (LUMO were 3.41, 3.19, 3.38 and 3.23 eV for SQD1, SQD2, SQD3, and SQD4, respectively. These values lie above the LUMO energy (−4.26 eV of the conduction band of TiO2 nanoparticles indicating possible electron injection from the excited dyes to the conduction band of the TiO2 in dye-sensitized solar cells (DSSCs. Also, aromaticity computation for these dyes are in good agreement with the data obtained optically and geometrically with SQD4 as the highest aromatic structure. Based on the optimized molecular geometries, relative positions of the frontier orbitals, and the absorption maxima, we propose that these dyes are suitable components of photovoltaic DSSC devices.

  19. DFT calculations on 1,4-dithiine and S-oxygenated derivatives

    Directory of Open Access Journals (Sweden)

    E. Vessally

    2008-12-01

    Full Text Available The molecular structures of 1,4-dithiine and S-oxygenated derivatives are studied using B3LYP/6-311++G** level of theory. These compounds have 8π-electrons in the ring. This led to stabilization of non-planar conformation. DFT calculations show that 1,4-dithiine, C4H4SS, 1,4-dithiine-1-oxide, C4H4SOS, 1,4-dithiine-1,4-dioxide, C4H4SOSO and 1,4-dithiine-1,1,4-trioxide, C4H4SO2SO; have boat conformation. 1,4-dithiine-1,1-dioxide, C4H4SO2S, have a shadow boat conformation. 1,4-dithiine-1,1,4,4-tetraoxide, C4H4SO2SO2, have a planar conformation.

  20. Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysis of 3,5 di tert butyl 4 hydroxy benzoic acid

    Science.gov (United States)

    Mathammal, R.; Sangeetha, K.; Sangeetha, M.; Mekala, R.; Gadheeja, S.

    2016-09-01

    In this study, we report a combined experimental and theoretical study on molecular structure and vibrational spectra of 3,5 di tert butyl 4 hydroxy benzoic acid. The properties of title compound have been evaluated by quantum chemical calculation (DFT) using B3LYP functional and 6-31 + G (d, p) as basis set. IR Spectra has been recorded using Fourier transform infrared spectroscopy (FT-IR) in the region 4000-400 cm-1. The vibrational assignment of the calculated normal modes has been made on the basis set. The isotropic chemical shifts computed by 13C and 1H NMR (Nuclear Magnetic Resonance) analyses also show good agreement with experimental observations. The theoretical UV-Vis spectrum of the compound are used to study the visible absorption maxima (λ max). The structure activity relationship have been interpreted by mapping electrostatic potential surface (MEP), which is valuable information for the quality control of medicines and drug receptor interactions. The Mullikan charges, HOMO (Highest Occupied Molecular Orbital) - LUMO (Lowest Unoccupied Molecular Orbital) energy are analyzed. HOMO-LUMO energy gap and other related molecular properties are also calculated. The Natural Bond Orbital (NBO) analysis is carried out to investigate the various intra and inter molecular interactions of molecular system. The Non-linear optical properties such as dipole moment (μ), polarizability (αtot) and molecular first order hyperpolarizability (β) of the title compound are computed with B3LYP/6-31 + G (d,p) level of theory.

  1. A theoretical study on 2-chloro-5-(2-hydroxyethyl-4-methoxy-6-methylpyrimidine by DFT/ab initio calculations

    Directory of Open Access Journals (Sweden)

    Gümüs Hacer Pir

    2015-06-01

    Full Text Available Quantum chemical calculations have been performed to study the molecular geometry, 1H and 13C NMR chemical shifts, conformational, natural bond orbital (NBO and nonlinear optical (NLO properties of the 2-chloro-5-(2-hydroxyethyl-4- methoxy-6-methylpyrimidine molecule in the ground state using DFT and HF methods with 6-311++G(d,p basis set. The optimized geometric parameters and 1H and 13C NMR chemical shifts have been compared with the experimental values of the title molecule. The results of the calculations show excellent agreement between the experimental and calculated frequencies at B3LYP/6-311++G(d,p level. In order to provide a full understanding of the properties of the title molecule in the context of molecular orbital picture, the highest occupied molecular energy level (EHOMO, the lowest unoccupied molecular energy level (ELUMO, the energy difference (DE between EHOMO and ELUMO, electronegativity (χ, hardness (η and softness (S have been calculated using B3LYP/6-311++G(d,p and HF/6-311++G(d,p levels. The calculated HOMO and LUMO energies show that the charge transfer occurs within the title molecule.

  2. A comparative study of MP2, B3LYP, RHF and SCC-DFTB force fields in predicting the vibrational spectra of N-acetyl-L-alanine-N'-methyl amide: VA and VCD spectra

    DEFF Research Database (Denmark)

    Bohr, Henrik; Jalkanen, Karl J.; Elstner, M.

    1999-01-01

    dichroism (VCD) spectra of NALANMA. We have utilised MP2/6-31G*, B3LYP/6-31G*, RHF/6-31G* and SCC-DFTB level theory to determine the geometries and Hessians, atomic polar tensors (APT) and atomic axial tensors (AAT) which are required for simulating the VA and VCD spectra. We have also calculated the AAT...

  3. Vacuum UV Polarization Spectroscopy of p-Terphenyl

    DEFF Research Database (Denmark)

    Nguyen, Duy Duc; Jones, Nykola C.; Hoffmann, Søren Vrønning

    2018-01-01

    functional theory(TD–DFT) procedures TD–CAM-B3LYP, TD–LC-wPBE, and TD–wB97XD are insimilar qualitative agreement with the observed partial absorbance curvesthroughout the investigated spectral regions, while TD–B3LYP fails to predictqualitatively the spectrum of p-terphenylin the region above 40000 cm–1 (250...

  4. DFT study on the standard electrode potentials of imidazole, tetrathiafulvalene, and tetrathiafulvalene-imidazole.

    Science.gov (United States)

    Tugsuz, Tugba

    2010-12-30

    Extensive DFT calculations on the standard electrode potentials of imidazole (Im), tetrathiafulvalene (TTF), and 2-, 4-, and 5-TTF-Im were carried out. Geometries and Gibbs free energies of H-bonded dimer, anion, protonated cation, and neutral structures of Im, mono- and dication, and neutral structures of TTF in gas and acetonitrile solvent were computed by using 10 hybrid density functionals (B3LYP, TPSSH, PBEH1PBE, M06, M062X, X3LYP, BMK, B1B95, M05, M052X) combined with the TZVP basis set. CPCM and SMD solvation models were applied to predict the Gibbs free energies of molecules in acetonitrile solvent. Frequency calculations were carried out for all structures, and none of them has been found to exhibit any imaginary frequency. Finally, the BMK hybrid functional was selected for computation of the standard electrode potential of TTF-Im, because it gives the most accurate values in both Im and TTF, differing by 0.05 V from the experimental ones. Moreover, frequencies from the BMK functional are reasonably close to the experimental ones. The standard electrode potentials of 2-, 4-, and 5-TTF-Im predicted for two-electron oxidation are 0.946, 0.870, and 0.839 V in CPCM and 0.927, 0.866, and 0.824 V in SMD. For one-electron oxidation these are 0.491, 0.421, and 0.400 V in CPCM and 0.476, 0.377, and 0.360 V in SMD, respectively.

  5. Study on the Reactivity of Amino Acid Chemosensor, NPFNP, with Ethanol: Structural Elucidation through Single Crystal XRD and DFT Calculations

    Directory of Open Access Journals (Sweden)

    Beena Varghese

    2017-01-01

    Full Text Available A novel ethoxy derivative of an amino acid chemosensor, 3-naphthyl-1-phenyl-5-(2ʹ-fluoro-5ʹ-nitrophenyl-2-pyrazoline (NPFNP, has been synthesized and characterized by different spectroscopic methods.  A single crystal of the ethoxy derivative, 3-naphthyl-1-phenyl-5-(2ʹ-ethoxy-5ʹ-nitrophenyl-2-pyrazoline NPENP, has been obtained and characterized.  The structure holds interest as it carries biologically active pyrazoline as a central ring attaching to electron donating and withdrawing substituents. The major motivation for this work was to gain detailed insight into the structural parameters of this compound for investigating the influence of crystal packing and geometrical dimensions on optical properties. Time-dependent DFT calculations have been employed for comparing the XRD data with theoretical parameters. The results show that the DFT method at B3LYP/6-31G level can well reproduce the structure of the title compound.

  6. Electronic and photophysical properties of 2-(2′-hydroxyphenyl)benzoxazole and its derivatives enhancing in the excited-state intramolecular proton transfer processes: A TD-DFT study on substitution effect

    Energy Technology Data Exchange (ETDEWEB)

    Daengngern, Rathawat; Kungwan, Nawee, E-mail: naweekung@gmail.com

    2015-11-15

    The effect of electron donating and withdrawing substituents on the enol absorption and keto emission spectra of 2-(2′-hydroxyphenyl)benzoxazole (HBO) and its derivatives has been systematically investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The enol absorption spectra of HBO were simulated by using five different DFTs with various exchange-correlation functions to validate a suitable functional prior to being further used as a method of choice to study the effect of substituents on the spectral characteristics of HBO derivatives. The popular B3LYP (Becke, three-parameter, Lee–Yang–Parr) exchange-correlation functional is found to provide the best desirable result in predicting the absorption spectrum close to experimental data. In the ground state, enol forms of HBO and its derivatives are more stable than those of keto forms, while in the first lowest excited state, keto forms are found to be more stable than their enol forms. Overall, simulated absorption and emission spectra of HBO and its derivatives from TD-B3LYP calculations are in good agreement with the experimental data. For enol, absorption maxima of HBO derivatives having electron-withdrawing groups are red-shift corresponding to their lower HOMO–LUMO energy gaps compared to that of HBO. For keto emission, HBO having electron donating groups (m-MeHBO and MHBO) and withdrawing group (CNHBO) at 4′-position on the phenol fragment as well as electron donating groups (HBOMe and HBOM) at 6-position on the benzoxazole fragment make the position of keto emission peak shift to shorter wavelength (blue-shift). However, HBO derivatives with electron withdrawing groups (HBOF, HBOCl, HBOA and HBOE) at 6-position give redshifted emission compared to the parent compound (HBO). The type of substituent on both 4′- and 6-positions certainly has a pronounced effect on the absorption and emission spectra of HBO derivatives. - Highlights: • Simulated spectra

  7. Electronic and photophysical properties of 2-(2′-hydroxyphenyl)benzoxazole and its derivatives enhancing in the excited-state intramolecular proton transfer processes: A TD-DFT study on substitution effect

    International Nuclear Information System (INIS)

    Daengngern, Rathawat; Kungwan, Nawee

    2015-01-01

    The effect of electron donating and withdrawing substituents on the enol absorption and keto emission spectra of 2-(2′-hydroxyphenyl)benzoxazole (HBO) and its derivatives has been systematically investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The enol absorption spectra of HBO were simulated by using five different DFTs with various exchange-correlation functions to validate a suitable functional prior to being further used as a method of choice to study the effect of substituents on the spectral characteristics of HBO derivatives. The popular B3LYP (Becke, three-parameter, Lee–Yang–Parr) exchange-correlation functional is found to provide the best desirable result in predicting the absorption spectrum close to experimental data. In the ground state, enol forms of HBO and its derivatives are more stable than those of keto forms, while in the first lowest excited state, keto forms are found to be more stable than their enol forms. Overall, simulated absorption and emission spectra of HBO and its derivatives from TD-B3LYP calculations are in good agreement with the experimental data. For enol, absorption maxima of HBO derivatives having electron-withdrawing groups are red-shift corresponding to their lower HOMO–LUMO energy gaps compared to that of HBO. For keto emission, HBO having electron donating groups (m-MeHBO and MHBO) and withdrawing group (CNHBO) at 4′-position on the phenol fragment as well as electron donating groups (HBOMe and HBOM) at 6-position on the benzoxazole fragment make the position of keto emission peak shift to shorter wavelength (blue-shift). However, HBO derivatives with electron withdrawing groups (HBOF, HBOCl, HBOA and HBOE) at 6-position give redshifted emission compared to the parent compound (HBO). The type of substituent on both 4′- and 6-positions certainly has a pronounced effect on the absorption and emission spectra of HBO derivatives. - Highlights: • Simulated spectra

  8. Benchmark Study of the Structural and Thermochemical Properties of a Dihydroazulene/Vinylheptafulvene Photoswitch

    DEFF Research Database (Denmark)

    Koerstz, Mads; Elm, Jonas; Mikkelsen, Kurt Valentin

    2017-01-01

    We investigate the performance of four different density functional theory (DFT) functionals (M06-2X, ωB97X-D, PBE0, and B3LYP-D3BJ) for calculating the structural and thermochemical properties of the dihydroazulene/vinylheptafulvene photoswitch (DHA/VHF). We find that all the tested DFT......, indicating that the largest source of error when calculating storage free energies originates from errors in the calculated single point energies. It was found that ωB97X-D and M06-2X performed decently for predicting storage energies. While B3LYP-D3BJ and PBE0 generally underestimated the storage energy...

  9. An efficient ab initio DFT and PCM assessment of the potentiometric selectivity of a salophen type Schiff base.

    Science.gov (United States)

    Demir, Serkan; Yilmaz, Hakan; Dilimulati, Maowulidan; Andaç, Müberra

    2014-06-01

    As a neutral carrier component for the preparation of a potentiometric membrane sensor, the affinity and selectivity of the salophen type Schiff base ligand obtained by 1:2 condensation of 2.3-diaminopyridine with salicylaldehyde toward a series of common cations has been fully examined by DFT/B3LYP and integral equation formalism polarizable continum model (IEF-PCM or only given with PCM as default input in the computations) in combination with the experimental data. Both the potentiometric measurements and DFT calculations have exhibited that the ionophore shows appreciable selectivity for Cu(2+) ion over other cations. Four different approaches where the last three are the modified version of each other have been evaluated and compared with potentiometric data. Based upon the results of comparison among the approaches suggested to verify the selective behavior of ionophore toward Cu(2+), PCM implemented approach having a whole computational groundwork has given well-matched results with the observed data and with the method augmented with experimental hydration energies. The foremost interferences were detected by determining potentiometric selectivity coefficients for each metal ion relative to Cu(2+) and compared to the results obtained by the DFT calculations.

  10. Benchmarking DFT and semi-empirical methods for a reliable and cost-efficient computational screening of benzofulvene derivatives as donor materials for small-molecule organic solar cells.

    Science.gov (United States)

    Tortorella, Sara; Talamo, Maurizio Mastropasqua; Cardone, Antonio; Pastore, Mariachiara; De Angelis, Filippo

    2016-02-24

    A systematic computational investigation on the optical properties of a group of novel benzofulvene derivatives (Martinelli 2014 Org. Lett. 16 3424-7), proposed as possible donor materials in small molecule organic photovoltaic (smOPV) devices, is presented. A benchmark evaluation against experimental results on the accuracy of different exchange and correlation functionals and semi-empirical methods in predicting both reliable ground state equilibrium geometries and electronic absorption spectra is carried out. The benchmark of the geometry optimization level indicated that the best agreement with x-ray data is achieved by using the B3LYP functional. Concerning the optical gap prediction, we found that, among the employed functionals, MPW1K provides the most accurate excitation energies over the entire set of benzofulvenes. Similarly reliable results were also obtained for range-separated hybrid functionals (CAM-B3LYP and wB97XD) and for global hybrid methods incorporating a large amount of non-local exchange (M06-2X and M06-HF). Density functional theory (DFT) hybrids with a moderate (about 20-30%) extent of Hartree-Fock exchange (HFexc) (PBE0, B3LYP and M06) were also found to deliver HOMO-LUMO energy gaps which compare well with the experimental absorption maxima, thus representing a valuable alternative for a prompt and predictive estimation of the optical gap. The possibility of using completely semi-empirical approaches (AM1/ZINDO) is also discussed.

  11. Benchmarking DFT and semi-empirical methods for a reliable and cost-efficient computational screening of benzofulvene derivatives as donor materials for small-molecule organic solar cells

    International Nuclear Information System (INIS)

    Tortorella, Sara; Talamo, Maurizio Mastropasqua; Cardone, Antonio; Pastore, Mariachiara; De Angelis, Filippo

    2016-01-01

    A systematic computational investigation on the optical properties of a group of novel benzofulvene derivatives (Martinelli 2014 Org. Lett. 16 3424–7), proposed as possible donor materials in small molecule organic photovoltaic (smOPV) devices, is presented. A benchmark evaluation against experimental results on the accuracy of different exchange and correlation functionals and semi-empirical methods in predicting both reliable ground state equilibrium geometries and electronic absorption spectra is carried out. The benchmark of the geometry optimization level indicated that the best agreement with x-ray data is achieved by using the B3LYP functional. Concerning the optical gap prediction, we found that, among the employed functionals, MPW1K provides the most accurate excitation energies over the entire set of benzofulvenes. Similarly reliable results were also obtained for range-separated hybrid functionals (CAM-B3LYP and wB97XD) and for global hybrid methods incorporating a large amount of non-local exchange (M06-2X and M06-HF). Density functional theory (DFT) hybrids with a moderate (about 20–30%) extent of Hartree–Fock exchange (HFexc) (PBE0, B3LYP and M06) were also found to deliver HOMO–LUMO energy gaps which compare well with the experimental absorption maxima, thus representing a valuable alternative for a prompt and predictive estimation of the optical gap. The possibility of using completely semi-empirical approaches (AM1/ZINDO) is also discussed. (paper)

  12. Synthesis, single crystal X-ray, spectroscopic (FT-IR, UV-vis, fluorescence, 1H &13C NMR), computational (DFT/B3LYP) studies of some imidazole based picrates

    Science.gov (United States)

    Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.; Selvanayagam, S.; Sridhar, B.

    2018-04-01

    2,4,5-triphenyl-1H-imidazol-3-ium picrate (1), 2-(4-fluorophenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (2), 2-(4-methylphenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (3) were synthesised. These compounds 1-3 were characterized by elemental, FT-IR, 1H NMR and 13C NMR analyses. The structure of compound 3 was further confirmed by single crystal X-ray diffraction. The studies reveal that the molecule is associated with weak Nsbnd H⋯O and Csbnd H⋯N and van der Waals interactions which are responsible for the formation and strengthening of supramolecular assembly. The nature of the interactions and their importance are explored using the Hirshfeld surface method. The physicochemical properties of the compounds 1-3 were evaluated by UV-vis spectroscopy, fluorescence spectroscopy, and thermogravimetric analysis. According to thermal data the salts possess excellent thermal stabilities with decomposition temperatures ranging from 220 to 280 °C. Second-harmonic generation (SHG) results exposed that the picrates 1-3 were about 1.13-1.50 times greater than potassium dihydrogen phosphate (KDP). Here we also used Density functional theory (DFT) calculations in order to investigate the opto-electronic properties. The obtained theoretical results validate with available experimental data.

  13. Synthesis, structural, photoluminescence, vibrational and DFT investigation of the bis (4-aminopyridinium) tetrachloridocuprate(II) monohydrate

    International Nuclear Information System (INIS)

    Kessentini, A.; Belhouchet, M.; Suñol, J.J.; Abid, Y.; Mhiri, T.

    2014-01-01

    The crystals of the family of alkylammonuim tetrachloridocuprate (II), (C 5 H 7 N 2 ) 2 CuCl 4 H 2 O, have been grown, structurally characterized and their vibrational as well as optical properties been studied. A preliminary single crystal X-ray diffraction structural analysis has revealed that the title compound belongs to the monoclinic system with space group C2/c. Its unit cell dimensions are: a=8.454 (2) Å, b=14.279 (2) Å, c=14.363 (3) Å, β=95.813 (4)°, with Z=4 and its crystal structure was determined and refined down to R 1 =0.029 and wR 2 =0.080. The crystal lattice is composed of discrete [CuCl 4 ] 2− tetrahedra surrounded by 4-aminopyridinium cations and water molecules which are interconnected by means of hydrogen bonding contacts [N–H…Cl, O–H…Cl and N–H…O]. Furthermore, the room temperature IR and Raman spectra of the title compound were recorded and analyzed. The optimized molecular structure and the vibrational spectra were calculated by the density functional theory (DFT) method using the B3LYP function. The organic–inorganic hybrid crystal thin film can be easily prepared by spin-coating method from the ethanol solution of the (C 5 H 7 N 2 ) 2 CuCl 4 H 2 O perovskite and it showed characteristic absorptions of CuCl-based layered perovskite centered at 288 and 400 nm, as well as the photoluminescence peak at around 443 nm. The unaided-eye-detectable blue luminescence emission comes from the excitonic transition in the CuCl 4 anions. - Highlights: • A new hybrid compound (C 5 H 7 N 2 ) 2 CuCl 4 H 2 O was synthesized. • Vibrational properties were studied by IR and Raman spectroscopy and examined theoretically using the DFT/B3LYP/LanL2DZ level of theory. • The UV–vis spectrum shows two absorption peaks at 288 and at 400 nm. • This compound show a strong blue emission at 443 nm

  14. DFT study of the interaction between 3-nitro-1,2,4-triazole-5-one and hydrogen fluoride

    International Nuclear Information System (INIS)

    Fang Guoyong; Xu Lina; Hu Xingen; Li Xinhua

    2008-01-01

    Three fully optimized geometries of 3-nitro-1,2,4-triazol-5-one-hydrogen fluoride (NTO-HF) complexes have been obtained with density functional theory (DFT) method at the B3LYP/6-311++G** level. The intermolecular interaction energy is calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction of the NTO-HF complexes is -34.155 kJ/mol. Electrons in complex systems transfer from NTO to HF. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. The strong hydrogen bonds contribute to the interaction energies dominantly. Frequency calculations are carried out on each optimized structure, and their IR spectra are discussed. Vibrational analysis show that there are large red-shifts for H-X (X = N and F) stretching vibrational frequencies in the NTO and hydrogen fluoride complexes. The changes of thermodynamic properties from the monomer to complexes with the temperature ranging from 200 K to 1500 K have been obtained using the statistical thermodynamic method. It is found that two of three NTO-HF complexes can be produced spontaneously from NTO and HF at room temperature

  15. DFT study of the interaction between 3-nitro-1,2,4-triazole-5-one and hydrogen fluoride

    Energy Technology Data Exchange (ETDEWEB)

    Fang Guoyong [College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035 (China); Xu Lina [College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035 (China)], E-mail: ahxulina@sohu.com; Hu Xingen; Li Xinhua [College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035 (China)

    2008-12-15

    Three fully optimized geometries of 3-nitro-1,2,4-triazol-5-one-hydrogen fluoride (NTO-HF) complexes have been obtained with density functional theory (DFT) method at the B3LYP/6-311++G** level. The intermolecular interaction energy is calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction of the NTO-HF complexes is -34.155 kJ/mol. Electrons in complex systems transfer from NTO to HF. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. The strong hydrogen bonds contribute to the interaction energies dominantly. Frequency calculations are carried out on each optimized structure, and their IR spectra are discussed. Vibrational analysis show that there are large red-shifts for H-X (X = N and F) stretching vibrational frequencies in the NTO and hydrogen fluoride complexes. The changes of thermodynamic properties from the monomer to complexes with the temperature ranging from 200 K to 1500 K have been obtained using the statistical thermodynamic method. It is found that two of three NTO-HF complexes can be produced spontaneously from NTO and HF at room temperature.

  16. Electronic structure investigations of 4-aminophthal hydrazide by UV-visible, NMR spectral studies and HOMO-LUMO analysis by ab initio and DFT calculations.

    Science.gov (United States)

    Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M

    2015-08-05

    Combined experimental and theoretical studies were conducted on the molecular structure and vibrational spectra of 4-AminoPhthalhydrazide (APH). The FT-IR and FT-Raman spectra of APH were recorded in the solid phase. The molecular geometry and vibrational frequencies of APH in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking 6-311+G(d,p) basis set. The optimized geometric bond lengths and bond angles obtained by HF and B3LYP method show best agreement with the experimental values. Comparison of the observed fundamental vibrational frequencies of APH with calculated results by HF and density functional methods indicates that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the NMR spectra of APH was also reported. The theoretical spectrograms for infrared and Raman spectra of the title molecule have been constructed. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. And the temperature dependence of the thermodynamic properties of constant pressure (Cp), entropy (S) and enthalpy change (ΔH0→T) for APH were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. CRADA/NFE-15-05761 Report: Additive Manufacturing of Isotropic NdFeB Bonded Permanent Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Paranthaman, M Parans [ORNL

    2016-07-18

    The technical objective of this technical collaboration phase I proposal is to fabricate net shape isotropic NdFeB bonded magnets utilizing additive manufacturing technologies at the ORNL MDF. The goal is to form complex shapes of thermoplastic and/or thermoset bonded magnets without expensive tooling and with minimal wasted material. Two additive manufacturing methods; the binder jet process; and big area additive manufacturing (BAAM) were used. Binder jetting produced magnets with the measured density of the magnet of 3.47 g/cm3, close to 46% relative to the NdFeB single crystal density of 7.6 g/cm3 were demonstrated. Magnetic measurements indicate that there is no degradation in the magnetic properties. In addition, BAAM was used to fabricate isotropic near-net-shape NdFeB bonded magnets with magnetic and mechanical properties comparable or better than those of traditional injection molded magnets. The starting polymer magnet composite pellets consist of 65 vol% isotropic NdFeB powder and 35 vol% polyamide (Nylon-12). The density of the final BAAM magnet product reached 4.8 g/cm3, and the room temperature magnetic properties are: Intrinsic coercivity Hci = 8.65 kOe, Remanence Br = 5.07 kG, and energy product (BH)max = 5.47 MGOe (43.50 kJ/m3). This study provides a new pathway for preparing near-net shape bonded magnets for various magnetic applications.

  18. X-ray, Hirshfeld surface analysis, spectroscopic and DFT studies of polycyclic aromatic hydrocarbons: Fluoranthene and acenaphthene

    Directory of Open Access Journals (Sweden)

    Śmiszek-Lindert Wioleta

    2015-01-01

    Full Text Available The X-ray structure, theoretical calculation, Hirshfeld surfaces analysis, IR and Raman spectra of fluoranthene and acenaphthene were reported. Acenaphthene crystallizes in the orthorhombic crystal system and space group P21ma, with crystal parameters a = 7.2053 (9 Å, b = 13.9800 (15 Å, c = 8.2638 (8 Å, Z = 4 and V = 832.41 (16 Å3. In turn, the grown crystals of fluoranthene are in monoclinic system with space group P21/n. The unit cell parameters are a = 18.3490 (2 Å, b = 6.2273 (5 Å, c = 19.8610 (2 Å, β = 109.787 (13°, Z = 8 and unit cell volume is 2135.50 (4 Å3. Theoretical calculations of the title compounds isolated molecule have been carried out using DFT at the B3LYP level. The intermolecular interactions in the crystal structure, for both the title PAHs, were analyzed using Hirshfeld surfaces computational method.

  19. Computational study of AuSi{sub n} (n=1-9) nanoalloy clusters invoking DFT based descriptors

    Energy Technology Data Exchange (ETDEWEB)

    Ranjan, Prabhat; Kumar, Ajay [Department of Mechatronics, Manipal University Jaipur Dehmi Kalan, Jaipur-303007 (India); Chakraborty, Tanmoy, E-mail: tanmoy.chakraborty@jaipur.manipal.edu, E-mail: tanmoychem@gmail.com [Department of Chemistry, Manipal University Jaipur Dehmi Kalan, Jaipur-303007 (India)

    2016-04-13

    Nanoalloy clusters formed between Au and Si are topics of great interest today from both scientific and technological point of view. Due to its remarkable catalytic, electronic, mechanical and magnetic properties Au-Si nanoalloy clusters have extensive applications in the field of microelectronics, catalysis, biomedicine, and jewelry industry. Density Functional Theory (DFT) is a new paradigm of quantum mechanics, which is very much popular to study the electronic properties of materials. Conceptual DFT based descriptors have been invoked to correlate the experimental properties of nanoalloy clusters. In this venture, we have systematically investigated AuSi{sub n} (n=1-9) nanoalloy clusters in the theoretical frame of the B3LYP exchange correlation. The experimental properties of AuSi{sub n} (n=1-9) nanoalloy clusters are correlated in terms of DFT based descriptors viz. HOMO-LUMO gap, Electronegativity (χ), Global Hardness (η), Global Softness (S) and Electrophilicity Index (ω). The calculated HOMO-LUMO gap exhibits interesting odd-even alteration behaviour, indicating that even numbered clusters possess higher stability as compare to their neighbour odd numbered clusters. This study also reflects a very well agreement between experimental bond length and computed data.

  20. Spectral Analysis of 3-(Adamantan-1-yl)-4-Ethyl-1-[(4-Phenylpiperazin-1-yl) Methyl]-1 H-1,2,4-Triazole-5(4 H)-Thione

    Science.gov (United States)

    Mindarava, Y. L.; Shundalau, M. B.; Al-Wahaibi, L. H.; El-Emam, A. A.; Matsukovich, A. S.; Gaponenko, S. V.

    2018-05-01

    Vibrational IR (3200-650 cm-1) and Raman spectra (3200-150 cm-1) of adamantane-containing 3-(adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione, which is promising for drug design, were examined. The UV/Vis spectrum (450-200 nm) of the compound in EtOH was measured. Full geometry optimization using density functional theory (DFT) in the B3LYP/cc-pVDZ approximation allowed the equilibrium configuration of the molecule to be determined and IR and Raman spectra to be calculated. Based on these, the experimental vibrational IR and Raman spectra were interpreted and the biological activity indices were predicted. The UV/Vis spectrum of the title compound was simulated at the time-dependent DFT/CAM-B3LYP/cc-pVDZ level with and without solvent effects and at the ab initio multi-reference perturbation theory XMCQDPT2 level. The UV/Vis spectrum that was simulated using the multi-reference XMCQDPT2 approximation agreed very successfully with the experimental data, in contrast to the single-reference DFT method. This was probably a consequence of intramolecular charge transfer.

  1. Spectral Analysis of 3-(Adamantan-1-yl)-4-Ethyl-1-[(4-Phenylpiperazin-1-yl) Methyl]-1H-1,2,4-Triazole-5(4H)-Thione

    Science.gov (United States)

    Mindarava, Y. L.; Shundalau, M. B.; Al-Wahaibi, L. H.; El-Emam, A. A.; Matsukovich, A. S.; Gaponenko, S. V.

    2018-05-01

    Vibrational IR (3200-650 cm-1) and Raman spectra (3200-150 cm-1) of adamantane-containing 3-(adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione, which is promising for drug design, were examined. The UV/Vis spectrum (450-200 nm) of the compound in EtOH was measured. Full geometry optimization using density functional theory (DFT) in the B3LYP/cc-pVDZ approximation allowed the equilibrium configuration of the molecule to be determined and IR and Raman spectra to be calculated. Based on these, the experimental vibrational IR and Raman spectra were interpreted and the biological activity indices were predicted. The UV/Vis spectrum of the title compound was simulated at the time-dependent DFT/CAM-B3LYP/cc-pVDZ level with and without solvent effects and at the ab initio multi-reference perturbation theory XMCQDPT2 level. The UV/Vis spectrum that was simulated using the multi-reference XMCQDPT2 approximation agreed very successfully with the experimental data, in contrast to the single-reference DFT method. This was probably a consequence of intramolecular charge transfer.

  2. The dynamics of molecular dimers in the crystals of m-aminobenzoic acid studied by inelastic neutron scattering (INS), Raman, IR spectroscopy and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Pawlukojc, A.; Leciejewicz, J

    2004-03-29

    Inelastic neutron scattering, Raman and IR spectra were measured for m-aminobenzoic acid (MABA). Optimized geometries and observed frequencies were assigned using DFT calculation on the B3LYP/6-311G** level using Gaussian 98 and Gamess programs. Experimental structural and spectroscopic data are in good agreement with computations assuming the presence in the crystals of molecular dimers composed of two MABA molecules linked by a pair of O-H...O hydrogen bonds each provided by the carboxylic group. INS frequencies have been identified for the O-H (out of plane) mod0008.

  3. ONIOM DFT/PM3 calculations on the interaction between dapivirine and HIV-1 reverse transcriptase, a theoretical study.

    Science.gov (United States)

    Liang, Y H; Chen, F E

    2007-08-01

    Theoretical investigations of the interaction between dapivirine and the HIV-1 RT binding site have been performed by the ONIOM2 (B3LYP/6-31G (d,p): PM3) and B3LYP/6-31G (d,p) methods. The results derived from this study indicate that this inhibitor dapivirine forms two hydrogen bonds with Lys101 and exhibits strong π-π stacking or H…π interaction with Tyr181 and Tyr188. These interactions play a vital role in stabilizing the NNIBP/dapivirine complex. Additionally, the predicted binding energy of the BBF optimized structure for this complex system is -18.20 kcal/mol.

  4. Molecular design of donor-acceptor dyes for efficient dye-sensitized solar cells I: a DFT study.

    Science.gov (United States)

    El-Shishtawy, Reda M; Asiri, Abdullah M; Aziz, Saadullah G; Elroby, Shaaban A K

    2014-06-01

    Dye-sensitized solar cells (DSSCs) have drawn great attention as low cost and high performance alternatives to conventional photovoltaic devices. The molecular design presented in this work is based on the use of pyran type dyes as donor based on frontier molecular orbitals (FMO) and theoretical UV-visible spectra in combination with squaraine type dyes as an acceptor. Density functional theory has been used to investigate several derivatives of pyran type dyes for a better dye design based on optimization of absorption, regeneration, and recombination processes in gas phase. The frontier molecular orbital (FMO) of the HOMO and LUMO energy levels plays an important role in the efficiency of DSSCs. These energies contribute to the generation of exciton, charge transfer, dissociation and exciton recombination. The computations of the geometries and electronic structures for the predicted dyes were performed using the B3LYP/6-31+G** level of theory. The FMO energies (EHOMO, ELUMO) of the studied dyes are calculated and analyzed in the terms of the UV-visible absorption spectra, which have been examined using time-dependent density functional theory (TD-DFT) techniques. This study examined absorption properties of pyran based on theoretical UV-visible absorption spectra, with comparisons between TD-DFT using B3LYP, PBE, and TPSSH functionals with 6-31+G (d) and 6-311++G** basis sets. The results provide a valuable guide for the design of donor-acceptor (D-A) dyes with high molar absorptivity and current conversion in DSSCs. The theoretical results indicated 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye (D2-Me) can be effectively used as a donor dye for DSSCs. This dye has a low energy gap by itself and a high energy gap with squaraine acceptor type dye, the design that reduces the recombination and improves the photocurrent generation in solar cell.

  5. Vibrational Spectroscopic Studies of Tenofovir Using Density Functional Theory Method

    Directory of Open Access Journals (Sweden)

    G. R. Ramkumaar

    2013-01-01

    Full Text Available A systematic vibrational spectroscopic assignment and analysis of tenofovir has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis was aided by electronic structure calculations—hybrid density functional methods (B3LYP/6-311++G(d,p, B3LYP/6-31G(d,p, and B3PW91/6-31G(d,p. Molecular equilibrium geometries, electronic energies, IR intensities, and harmonic vibrational frequencies have been computed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties such as HOMO and LUMO energies and were determined by time-dependent DFT (TD-DFT method. The geometrical, thermodynamical parameters, and absorption wavelengths were compared with the experimental data. The B3LYP/6-311++G(d,p-, B3LYP/6-31G(d,p-, and B3PW91/6-31G(d,p-based NMR calculation procedure was also done. It was used to assign the 13C and 1H NMR chemical shift of tenofovir.

  6. Probing the adsorption mechanism in thiamazole bound to the silver surface with Surface-enhanced Raman Scattering and DFT

    Science.gov (United States)

    Biswas, Nandita; Thomas, Susy; Sarkar, Anjana; Mukherjee, Tulsi; Kapoor, Sudhir

    2009-09-01

    Surface-enhanced Raman scattering (SERS) of thiamazole have been investigated in aqueous solution. Thiamazole is an important anti-thyroid drug that is used in the treatment of hyperthyroidism (over activity of the thyroid gland). Due to its medicinal importance, the surface adsorption properties of thiamazole have been studied. The experimental Raman and SERS data are supported with DFT calculations using B3LYP functional with LANL2DZ basis set. From the SERS spectra as well as theoretical calculations, it has been inferred that thiamazole is chemisorbed to the silver surface directly through the sulphur atom and the ring N atom, with a tilted orientation.

  7. Estimation of ΔR/R values by benchmark study of the Mössbauer Isomer shifts for Ru, Os complexes using relativistic DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Masashi [Japan Atomic Energy Agency, Nuclear Science and Engineering Center (Japan); Yasuhara, Hiroki; Miyashita, Sunao; Nakashima, Satoru, E-mail: snaka@hiroshima-u.ac.jp [Hiroshima University, Graduate School of Science (Japan)

    2017-11-15

    The present study applies all-electron relativistic DFT calculation with Douglas-Kroll-Hess (DKH) Hamiltonian to each ten sets of Ru and Os compounds. We perform the benchmark investigation of three density functionals (BP86, B3LYP and B2PLYP) using segmented all-electron relativistically contracted (SARC) basis set with the experimental Mössbauer isomer shifts for {sup 99}Ru and {sup 189}Os nuclides. Geometry optimizations at BP86 theory of level locate the structure in a local minimum. We calculate the contact density to the wavefunction obtained by a single point calculation. All functionals show the good linear correlation with experimental isomer shifts for both {sup 99}Ru and {sup 189}Os. Especially, B3LYP functional gives a stronger correlation compared to BP86 and B2PLYP functionals. The comparison of contact density between SARC and well-tempered basis set (WTBS) indicated that the numerical convergence of contact density cannot be obtained, but the reproducibility is less sensitive to the choice of basis set. We also estimate the values of ΔR/R, which is an important nuclear constant, for {sup 99}Ru and {sup 189}Os nuclides by using the benchmark results. The sign of the calculated ΔR/R values is consistent with the predicted data for {sup 99}Ru and {sup 189}Os. We obtain computationally the ΔR/R values of {sup 99}Ru and {sup 189}Os (36.2 keV) as 2.35×10{sup −4} and −0.20×10{sup −4}, respectively, at B3LYP level for SARC basis set.

  8. Exploring the structure-activity relations of N-carbethoxyphthalimide by combining FTIR, FT-Raman and NMR spectroscopy with DFT electronic structure method.

    Science.gov (United States)

    Arjunan, V; Govindaraja, S Thillai; Ravindran, P; Mohan, S

    2014-01-01

    The complete vibrational assignment and analysis of N-carbethoxyphthalimide were carried out using the experimental FTIR and FT-Raman data in the range 4000-450 and 4000-100 cm(-1), respectively along with quantum chemical studies of the compound using DFT-B3LYP gradient calculations employing the 6-31G**, 6-311++G** and cc-pVDZ basis sets. The 1H (400 MHz; CDCl3) and 13C (100 MHz;CDCl3) nuclear magnetic resonance (NMR) spectra were also recorded. Due to the partial ionic nature of the carbonyl group, the carbon atoms C1 and C3 in NCEP show downfield effect and the corresponding observed chemical shift of both are observed at 163.76 ppm and the carbon atom C16 in the carbethoxy group also give signal in the downfield at 148.45 ppm. The active sites are determined by molecular electrostatic potential. The possible electronic transitions are determined by HOMO and LUMO orbital shapes and their energies. The structure-chemical reactivity relations of the compound were determined through chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Spectroscopic data of Labdane Diterpenes: a theoretical analysis via NMR and DFT

    International Nuclear Information System (INIS)

    Souza, Fabrine S. de; Silva, Silvana de O.; Alves, Cláudio N.; Guilhon, Giselle M.S.P.

    2015-01-01

    Labdane diterpenes exhibit important bioactivities such as cardiovascular effects in rats as well as effects in the treatment of autoimmune diseases and Alzheimer syndrome. Recently, the labdane diterpenes ent-13-epi-manoil oxide, ribenone and ribenol were isolated from Croton palanostigma. The computational method DFT/B3LYP/cc-pVDZ was used to optimize the structures of these diterpenes and to calculate infrared data. Chemical shifts (δ H and δ C ) of the minimum energy structures (local minimum) were calculated and compared with the experimental data. Comparison of the NMR data by simple linear regression (SLR) showed satisfactory statistical results with a correlation coefficient (R 2 ) and predictive ability (Q 2 ) of over 98%. The predicted NMR data were used to confirm the δ H values that have not been published. (author)

  10. Theoretical Calculation of Jet Fuel Thermochemistry. 1; Tetrahydrodicylopentadiene (JP10) Thermochemistry Using the CBS-QB3 and G3(MP2)//B3LYP Methods

    Science.gov (United States)

    Zehe, Michael J.; Jaffe, Richard L.

    2010-01-01

    High-level ab initio calculations have been performed on the exo and endo isomers of gas-phase tetrahydrodicyclopentadiene (THDCPD), a principal component of the jet fuel JP10, using the Gaussian Gx and Gx(MPx) composite methods, as well as the CBS-QB3 method, and using a variety of isodesmic and homodesmotic reaction schemes. The impetus for this work is to help resolve large discrepancies existing between literature measurements of the formation enthalpy Delta (sub f)H deg (298) for exo-THDCPD. We find that use of the isodesmic bond separation reaction C10H16 + 14CH4 yields 12C2H6 yields results for the exo isomer (JP10) in between the two experimentally accepted values, for the composite methods G3(MP2), G3(MP2)//B3LYP, and CBS-QB3. Application of this same isodesmic bond separation scheme to gas-phase adamantane yields a value for Delta (sub f)H deg (298) within 5 kJ/mol of experiment. Isodesmic bond separation calculations for the endo isomer give a heat of formation in excellent agreement with the experimental measurement. Combining our calculated values for the gas-phase heat of formation with recent measurements of the heat of vaporization yields recommended values for Delta (sub f)H deg (298)liq of -126.4 and -114.7 kJ/mol for the exo and endo isomers, respectively.

  11. Crystal structure, vibrational and DFT simulation studies of melaminium dihydrogen phosphite monohydrate

    Science.gov (United States)

    Arjunan, V.; Kalaivani, M.; Marchewka, M. K.; Mohan, S.

    2013-08-01

    The crystal structure investigations of melamine with phosphorous acid, namely melaminium dihydrogenphosphite monohydrate (C3N6H7·H2PO3·H2O) have been investigated by means of single crystal X-ray diffraction method. The title compound crystallizes in monoclinic crystal system, and the space group is P21/c with a = 10.069 Å, b = 21.592 Å, c = 12.409 Å and Z = 12. The vibrational assignments and analysis of melaminium dihydrogen phosphite monohydrate have also been performed by FTIR, FT-Raman and far-infrared spectral studies. The quantum chemical simulations were performed with DFT (B3LYP) method using 6-31G**, cc-pVTZ, and 6-311++G** basis sets to determine the energy, structural, thermodynamic parameters and vibrational frequencies of melaminium dihydrogen phosphite monohydrate. The hydrogen atom from phosphorous acid was transferred to the melamine molecule giving the singly protonated melaminium cation. The ability of ions to form spontaneous three-dimensional structure through weak Osbnd H···O and Nsbnd H···O hydrogen bonds shows notable vibrational effects.

  12. FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule.

    Science.gov (United States)

    Muthu, S; Elamurugu Porchelvi, E

    2013-11-01

    The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed. Copyright © 2013 Elsevier B

  13. 1,7-Cyclization of 1-diazo-2,4-pentadiene and its heteroanalogues: DFT study

    Science.gov (United States)

    Subbotina, Julia O.; Bakulev, V. A.; Herges, R.; Fabian, W. M. F.

    1,7-Dipolar cyclizations of 1-diazo-2,4-pentadiene 1a and its heteroanalogues 1b,c and 4c were studied using density functional theory (DFT). Although the heteroanalogue 1c has an appropriate electronic structure to allow for pseudopericyclic cyclization, natural bond order (NBO) analysis has provided evidence for the electrocyclic ring closure. Magnetic criteria (anisotropy of the induced current density [ACID], nucleus-independent chemical shifts [NICS]) confirmed the pericyclic character of the located transition states 2a,c and 5c. The activation barriers for the cyclization of 1-diazo-2,4-pentadiene 1a and its aza analogues 1c, 4c are 3.3, 8.2, and 12.3 kcal/mol at the B3LYP/6-31G(d) level, respectively. The higher barrier of the 1c?3c and 4c?3c reactions compared with 1a?3a is in line with the Hammond postulate. The out-of-plane distorted geometry of the cyclic product is an additional factor arguing against a pseudopericyclic mechanism.

  14. Donor Acceptor Bond in [NPCl2]3—MCl3 Adducts, a DFT Study and Comparison of Results with Experimental X-Ray Data

    Directory of Open Access Journals (Sweden)

    Alireza Akbari

    2012-01-01

    Full Text Available Molecular structures of [PCl2N]3-MCl3 adducts, M=B, Al, Ga, In, Tl, have been studied employing HF, B3LYP*, B3LYP , PW91, BLYP, OLYP, BP and LDA methods using DZP basis set (as defined in Amsterdam Density Functional, ADF, package. Some aspects of adduct formation like considering the difference between Front and Back dihedral angles and also ring puckering showed that the [PCl2N]3-AlCl3 is the most stable adduct comparing the others. Based on the comparison between the X-ray and theoretical geometrical parameters of [NPCl2]3(AlCl3 and [NPCl2]3(GaCl3, the LDA method and BP, PW91 and OLYP functionals combined with DZP basis set were found to yield the most satisfactory agreement. Results showed that with surprise, the LDA(DZP method has the maximum matching with experimental data, comparing the others.

  15. Adsorption of alanine with heteroatom substituted fullerene for solar cell application: A DFT study.

    Science.gov (United States)

    Dheivamalar, S; Sugi, L; Ravichandran, K; Sriram, S

    2018-05-14

    C 20 is the most important fullerene cage and alanine is the simplest representation of a backbone unit of the protein. The absorption feasibility of alanine molecule in the Si-doped C 20 and B-doped C 20 fullerenes has been studied based on calculated electronic properties of fullerenes using density functional theory (DFT). In this work, we explore the ability of Si-doped C 20 , B-doped C 20 fullerene to interact with alanine at the DFT-B3LYP/6-31G, RHF level of theory. We find that noticeable structural change takes place in C 20 when one of its carbon is substituted with Si or B. The molecular geometry, electronic properties and vibrational analysis have also been performed on the title compounds. The NMR study reveals the aromaticity of the pure and doped fullerene compounds. Stability of the doped fullerene - alanine compound arises from hyper conjugative interactions. It leads to one of the major property of bioactivity, charge transfer and delocalization of charge and this properties has been analyzed using Natural Bond Orbital (NBO) analysis. The energy gap of the doped fullerene reveals that there is a decrease in the size of energy gap significantly, making them more reactive as compared to C 20 fullerene. Theoretical studies of the electronic spectra by using time - dependent density functional theory (TD-DFT) method were helpful to interpret the observed electronic transition state. We aim to optimize the performance of the solar cells by altering the frontier orbital energy gaps. Considering all studied properties, it may be inferred that the applicability of C 20 fullerene as the non-linear optical (NLO) material and its NLO property would increase on doping fullerene with Si and B atom. Specifically C 19 Si would be better among them. Copyright © 2018. Published by Elsevier B.V.

  16. The DFT calculations of structures and EPR parameters for the dinuclear paddle-wheel copper(II) complex {Cu_2(μ_2-O_2CCH_3)_4}(OCNH{sub 2}CH{sub 3}) as powder or single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua [Univ. of Electronic Science and Technology of China, Chengdu (China). School of Physical Electronics

    2017-07-01

    Density functional theory (DFT) calculations of the structures and the Cu{sup 2+} g factors (g{sub x}, g{sub y} and g{sub z}) and hyperfine coupling tensor A (A{sub x}, A{sub y} and A{sub z}) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu_2(μ_2-O_2CCH_3)_4}(OCNH{sub 2}CH{sub 3}) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO{sub 5}] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO{sub 5}] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH{sub 2}CH{sub 3}, NH{sub 3} and H{sub 2}O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  17. Quantum Mechanical Calculation of Noncovalent Interactions: A Large-Scale Evaluation of PMx, DFT, and SAPT Approaches.

    Science.gov (United States)

    Li, Amanda; Muddana, Hari S; Gilson, Michael K

    2014-04-08

    Quantum mechanical (QM) calculations of noncovalent interactions are uniquely useful as tools to test and improve molecular mechanics force fields and to model the forces involved in biomolecular binding and folding. Because the more computationally tractable QM methods necessarily include approximations, which risk degrading accuracy, it is essential to evaluate such methods by comparison with high-level reference calculations. Here, we use the extensive Benchmark Energy and Geometry Database (BEGDB) of CCSD(T)/CBS reference results to evaluate the accuracy and speed of widely used QM methods for over 1200 chemically varied gas-phase dimers. In particular, we study the semiempirical PM6 and PM7 methods; density functional theory (DFT) approaches B3LYP, B97-D, M062X, and ωB97X-D; and symmetry-adapted perturbation theory (SAPT) approach. For the PM6 and DFT methods, we also examine the effects of post hoc corrections for hydrogen bonding (PM6-DH+, PM6-DH2), halogen atoms (PM6-DH2X), and dispersion (DFT-D3 with zero and Becke-Johnson damping). Several orders of the SAPT expansion are also compared, ranging from SAPT0 up to SAPT2+3, where computationally feasible. We find that all DFT methods with dispersion corrections, as well as SAPT at orders above SAPT2, consistently provide dimer interaction energies within 1.0 kcal/mol RMSE across all systems. We also show that a linear scaling of the perturbative energy terms provided by the fast SAPT0 method yields similar high accuracy, at particularly low computational cost. The energies of all the dimer systems from the various QM approaches are included in the Supporting Information, as are the full SAPT2+(3) energy decomposition for a subset of over 1000 systems. The latter can be used to guide the parametrization of molecular mechanics force fields on a term-by-term basis.

  18. Theoretical investigation of molecular structure and vibrational spectra of 4,5-bis-(2-isopropyl-5- methylphenoxy) phthalonitrile molecule

    International Nuclear Information System (INIS)

    Avci, D.

    2005-01-01

    The molecular geometry and vibrational frequencies of 4,5-bis-(2-isopropyl-5- methylphenoxy) phthalonitrile in the ground state have been calculated using the Hartree- Fock (HF) and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP) show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of 4,5-bis-(2-isopropyl-5-methylphenoxy) phthalonitrile with calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems

  19. Ab initio hybrid DFT calculations of BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Eglitis, Roberts I., E-mail: rieglitis@gmail.com

    2015-12-15

    Highlights: • Surface energies for AO{sub 3}-term (111) surfaces are larger than for Ti (Zr)-term surfaces. • A increase of Ti−O (Zr−O) bond covalency near the ABO{sub 3} (111) surface relative to the bulk is observed. • The ABO{sub 3} (111) surface energy is larger than the earlier calculated (001) surface energy. • Band gap for PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces becomes smaller, but for BaTiO{sub 3} (111) larger with respect to the bulk . - Abstract: The results of ab initio calculations for polar BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces using the CRYSTAL code are presented. By means of the hybrid B3LYP approach, the surface relaxation has been calculated for two possible B (B = Ti or Zr) or AO{sub 3} (A = Ba, Pb or Sr) BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surface terminations. According to performed B3LYP calculations, all atoms of the first surface layer, for both terminations, relax inwards. The only exception is a small outward relaxation of the PbO{sub 3}-terminated PbTiO{sub 3} (111) surface upper layer Pb atom. B3LYP calculated surface energies for BaO{sub 3}, PbO{sub 3}, SrO{sub 3} and PbO{sub 3}-terminated BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces are considerably larger than the surface energies for Ti (Zr)-terminated (111) surfaces. Performed B3LYP calculations indicate a considerable increase of Ti−O (Zr−O) chemical bond covalency near the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surface relative to the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} bulk. Calculated band gaps at the Γ-point near the PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} (111) surfaces are reduced, but near BaTiO{sub 3} (111) surfaces increased, with respect to the BaTiO{sub 3}, PbTiO{sub 3}, SrZrO{sub 3} and PbZrO{sub 3} bulk band gap at the Γ-point values.

  20. DFT calculations on electronic properties of ZnO thin films deposited by spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Cordeiro, J.M.; Reynoso, V.C.; Azevedo, D.H.M. [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), SP (Brazil)

    2016-07-01

    Full text: Introduction - Thin films of Zinc oxide (ZnO) has a wide range of technological applications, as transparent conducting electrodes in solar cells, flat panel displays, and sensors, for example. More recently applications in optoelectronics, like light emitter diodes and laser diodes, due to its large band gap, are been explored. Studies of ZnO thin films are important for these applications. Methodology - In this study thin films of ZnO have been deposited by spray pyrolysis on glass substrate. The films were characterized by XRD and UV-VIS techniques and the electronic properties as a function of the film thickness have been investigated by DFT calculations with B3LYP hybrid potential implemented in the CRYSTAL09 code. Results - The diffractograms obtained for the ZnO thin films as a function of the thickness are shown. The films exhibit a hexagonal wurtzite structure with preferred c-axis orientation in (002) direction of ZnO crystal. A quantum mechanical approach based on the periodic Density Functional Theory (DFT), with B3LYP hybrid potential was used to investigate the electronic structure of the films as a function of the thickness. The CRYSTAL09 code has been used for the calculations on the wurtzite hexagonal structure of ZnO - spatial group P63mc. For optimizing the geometry of the pure ZnO crystal, the experimental lattice parameters were got as follows: a= 0.325 nm, b= 0.325 nm, c= 0.5207 nm with c/a= 1.602. Considering to the calculations of the band structure, it is suggested that the semiconducting properties of ZnO arises from the overlapping of the 4s orbital of the conducting band of Zn and the 2p orbital of the top of valence band of O. Conclusions - The structure of ZnO thin film deposited on glass substrate present preferential orientation in (002) direction. Variation in the optical properties as a function of the film thickness was observed. The band gap energy was determined from optical analysis to be ∼ 3.27 eV. The refractive

  1. Molecular Geometry And Vibrational Spectra of 2'-chloroacetanilide

    International Nuclear Information System (INIS)

    Gokce, H.

    2008-01-01

    The molecular structure, vibrational frequencies and the corresponding vibrational assingments of 2'-chloroacetanilide in the ground state have been calculated by using Hartree-Fock (HF) and Density Functional Theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set. The obtained vibrational frequencies and optimized geometric parameters (bond lenghts and angles) are in very good agreement with the experimental data. The comparison of the observed and calculated vibrational frequencies assignments of 2'-chloroacetanilide exhibit that the scaled DFT/B3LYP method is superior to be scaled HF method. Furthermore the calculated Infrared and Raman intensities are also reported

  2. Surface enhancement Raman scattering of tautomeric thiobarbituric acid. Natural bond orbitals and B3LYP/6-311+G (d, p) assignments of the Fourier Infrared and Fourier Raman Spectra.

    Science.gov (United States)

    Soto, C A Téllez; Ramos, J M; Costa Junior, A C; Vieira, Laís S; Rangel, João L; Raniero, L; Fávero, Priscila P; Lemma, Tibebe; Ondar, Grisset F; Versiane, Otavio; Martin, A A

    2013-10-01

    Surface enhancement Raman scattering (SERS) of two tautomer of thiobarbituric acid was obtained using silver and gold nanoparticles. Large band enhancement in the region of the ν(C=S), ν(C=C), δ(CH2), and δ(CNH) vibrational modes was found. Natural bond analysis of the tautomer species revealed expressive values of charge transfer, principally from lone pair electron orbitals of the S, N, and O atoms. Complete vibrational assignment was done for the two tautomers using the B3LYP/6-311+G (d, p) procedure, band deconvolution analysis, and from a rigorous interpretation of the normal modes matrix. The calculated spectra agree well with the experimental ones. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Molecular vibrational investigation [FT-IR, FT-Raman, UV-Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations

    Science.gov (United States)

    Anand, S.; Sundararajan, R. S.; Ramachandraraja, C.; Ramalingam, S.; Durga, R.

    2015-03-01

    In the present research work, the FT-IR, FT-Raman spectra of the Bis(thiourea) Nickel chloride (BTNC) were recorded and analyzed. The observed fundamental frequencies in finger print and functional group regions were assigned according to their uniqueness region. The computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The present organo-metallic compound was made up of covalent and coordination covalent bonds. The modified vibrational pattern of the complex molecule associated with ligand group was analyzed. Furthermore, the 13C NMR and 1H NMR spectral data were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP/6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A investigation on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed.

  4. Importance of the Electron Correlation and Dispersion Corrections in Calculations Involving Enamines, Hemiaminals, and Aminals. Comparison of B3LYP, M06-2X, MP2, and CCSD Results with Experimental Data.

    Science.gov (United States)

    Castro-Alvarez, Alejandro; Carneros, Héctor; Sánchez, Dani; Vilarrasa, Jaume

    2015-12-18

    While B3LYP, M06-2X, and MP2 calculations predict the ΔG° values for exchange equilibria between enamines and ketones with similar acceptable accuracy, the M06-2X/6-311+G(d,p) and MP2/6-311+G(d,p) methods are required for enamine formation reactions (for example, for enamine 5a, arising from 3-methylbutanal and pyrrolidine). Stronger disagreement was observed when calculated energies of hemiaminals (N,O-acetals) and aminals (N,N-acetals) were compared with experimental equilibrium constants, which are reported here for the first time. Although it is known that the B3LYP method does not provide a good description of the London dispersion forces, while M06-2X and MP2 may overestimate them, it is shown here how large the gaps are and that at least single-point calculations at the CCSD(T)/6-31+G(d) level should be used for these reaction intermediates; CCSD(T)/6-31+G(d) and CCSD(T)/6-311+G(d,p) calculations afford ΔG° values in some cases quite close to MP2/6-311+G(d,p) while in others closer to M06-2X/6-311+G(d,p). The effect of solvents is similarly predicted by the SMD, CPCM, and IEFPCM approaches (with energy differences below 1 kcal/mol).

  5. Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate

    Science.gov (United States)

    Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.

    2015-06-01

    Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by 1H and 13C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358 K for heating and cooling, respectively.

  6. Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline

    Science.gov (United States)

    Hernández-Paredes, Javier; Hernández-Negrete, Ofelia; Carrillo-Torres, Roberto C.; Sánchez-Zeferino, Raúl; Duarte-Moller, Alberto; Alvarez-Ramos, Mario E.

    2015-10-01

    2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good β values. However, the β values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline.

  7. Quantum mechanical and spectroscopic (FT-IR, 13C, 1H NMR and UV) investigations of 2-(5-(4-Chlorophenyl)-3-(pyridin-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole by DFT method

    Science.gov (United States)

    Diwaker

    2014-07-01

    The electronic, NMR, vibrational, structural properties of a new pyrazoline derivative: 2-(5-(4-Chlorophenyl)-3-(pyridine-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole has been studied using Gaussian 09 software package. Using VEDA 4 program we have reported the PED potential energy distribution of normal mode of vibrations of the title compound. We have also reported the 1H and 13C NMR chemical shifts of the title compound using B3LYP level of theory with 6-311++G(2d,2p) basis set. Using time dependent (TD-DFT) approach electronic properties such as HOMO and LUMO energies, electronic spectrum of the title compound has been studied and reported. NBO analysis and MEP surface mapping has also been calculated and reported using ab initio methods.

  8. Synthesis, structural, photoluminescence, vibrational and DFT investigation of the bis (4-aminopyridinium) tetrachloridocuprate(II) monohydrate

    Energy Technology Data Exchange (ETDEWEB)

    Kessentini, A., E-mail: kessentiniabir@gmail.com [Laboratoire Physico-Chimie de l’Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia); Belhouchet, M. [Laboratoire Physico-Chimie de l’Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia); Suñol, J.J. [Departamento De Fisica, Universita de Girona, Compus Montilivi, Girona 17071 (Spain); Abid, Y. [Laboratoire de Physique appliquée, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia); Mhiri, T. [Laboratoire Physico-Chimie de l’Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia)

    2014-05-01

    The crystals of the family of alkylammonuim tetrachloridocuprate (II), (C{sub 5}H{sub 7}N{sub 2}){sub 2}CuCl{sub 4}H{sub 2}O, have been grown, structurally characterized and their vibrational as well as optical properties been studied. A preliminary single crystal X-ray diffraction structural analysis has revealed that the title compound belongs to the monoclinic system with space group C2/c. Its unit cell dimensions are: a=8.454 (2) Å, b=14.279 (2) Å, c=14.363 (3) Å, β=95.813 (4)°, with Z=4 and its crystal structure was determined and refined down to R{sub 1}=0.029 and wR{sub 2}=0.080. The crystal lattice is composed of discrete [CuCl{sub 4}]{sup 2−} tetrahedra surrounded by 4-aminopyridinium cations and water molecules which are interconnected by means of hydrogen bonding contacts [N–H…Cl, O–H…Cl and N–H…O]. Furthermore, the room temperature IR and Raman spectra of the title compound were recorded and analyzed. The optimized molecular structure and the vibrational spectra were calculated by the density functional theory (DFT) method using the B3LYP function. The organic–inorganic hybrid crystal thin film can be easily prepared by spin-coating method from the ethanol solution of the (C{sub 5}H{sub 7}N{sub 2}){sub 2}CuCl{sub 4}H{sub 2}O perovskite and it showed characteristic absorptions of CuCl-based layered perovskite centered at 288 and 400 nm, as well as the photoluminescence peak at around 443 nm. The unaided-eye-detectable blue luminescence emission comes from the excitonic transition in the CuCl{sub 4} anions. - Highlights: • A new hybrid compound (C{sub 5}H{sub 7}N{sub 2}){sub 2}CuCl{sub 4}H{sub 2}O was synthesized. • Vibrational properties were studied by IR and Raman spectroscopy and examined theoretically using the DFT/B3LYP/LanL2DZ level of theory. • The UV–vis spectrum shows two absorption peaks at 288 and at 400 nm. • This compound show a strong blue emission at 443 nm.

  9. Intramolecular BSSE and dispersion affect the structure of a dipeptide conformer

    Science.gov (United States)

    Hameed, Rabia; Khan, Afsar; van Mourik, Tanja

    2018-05-01

    B3LYP and MP2 calculations with the commonly-used 6-31+G(d) basis set predict qualitatively different structures for the Tyr-Gly conformer book1, which is the most stable conformer identified in a previous study. The structures differ mainly in the ψtyr Ramachandran angle (138° in the B3LYP structure and 120° in the MP2 structure). The causes for the discrepant structures are attributed to missing dispersion in the B3LYP calculations and large intramolecular BSSE in the MP2 calculations. The correct ψtyr value is estimated to be 130°. The MP2/6-31+G(d) profile identified an additional conformer, not present on the B3LYP surface, with a ψtyr value of 96° and a more folded structure. This minimum is, however, likely an artefact of large intramolecular BSSE values. We recommend the use of basis sets of at least quadruple-zeta quality in density functional theory (DFT), DFTaugmented with an empirical dispersion term (DFT-D) and second-order Møller-Plesset perturbation theory (MP2 ) calculations in cases where intramolecular BSSE is expected to be large.

  10. Molecular vibrational investigation [FT-IR, FT-Raman, UV-Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations.

    Science.gov (United States)

    Anand, S; Sundararajan, R S; Ramachandraraja, C; Ramalingam, S; Durga, R

    2015-03-05

    In the present research work, the FT-IR, FT-Raman spectra of the Bis(thiourea) Nickel chloride (BTNC) were recorded and analyzed. The observed fundamental frequencies in finger print and functional group regions were assigned according to their uniqueness region. The computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The present organo-metallic compound was made up of covalent and coordination covalent bonds. The modified vibrational pattern of the complex molecule associated with ligand group was analyzed. Furthermore, the (13)C NMR and (1)H NMR spectral data were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP/6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A investigation on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

  11. Spectroscopic [FT-IR and FT-Raman] and theoretical [UV-Visible and NMR] analysis on α-Methylstyrene by DFT calculations

    Science.gov (United States)

    Karthikeyan, N.; Joseph Prince, J.; Ramalingam, S.; Periandy, S.

    2015-05-01

    In the present research work, the FT-IR, FT-Raman and 13C and 1H NMR spectra of the α-Methylstyrene were recorded. The observed fundamental frequencies in finger print as well as functional group regions were assigned according to their uniqueness region. The Gaussian computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The impact of the presence of vinyl group in phenyl structure of the compound is investigated. The modified vibrational pattern of the molecule associated vinyl group was analyzed. Moreover, 13C NMR and 1H NMR were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed.

  12. Molecular structures of Se(SCH3)2 and Te(SCH3)2 using gas-phase electron diffraction and ab initio and DFT geometry optimisations.

    Science.gov (United States)

    Fleischer, Holger; Wann, Derek A; Hinchley, Sarah L; Borisenko, Konstantin B; Lewis, James R; Mawhorter, Richard J; Robertson, Heather E; Rankin, David W H

    2005-10-07

    The molecular structures of Se(SCH(3))(2) and Te(SCH(3))(2) were investigated using gas-phase electron diffraction (GED) and ab initio and DFT geometry optimisations. While parameters involving H atoms were refined using flexible restraints according to the SARACEN method, parameters that depended only on heavy atoms could be refined without restraints. The GED-determined geometric parameters (r(h1)) are: rSe-S 219.1(1), rS-C 183.2(1), rC-H 109.6(4) pm; angleS-Se-S 102.9(3), angleSe-S-C 100.6(2), angleS-C-H (mean) 107.4(5), phiS-Se-S-C 87.9(20), phiSe-S-C-H 178.8(19) degrees for Se(SCH(3))(2), and rTe-S 238.1(2), rS-C 184.1(3), rC-H 110.0(6) pm; angleS-Te-S 98.9(6), angleTe-S-C 99.7(4), angleS-C-H (mean) 109.2(9), phiS-Te-S-C 73.0(48), phiTe-S-C-H 180.1(19) degrees for Te(SCH(3))(2). Ab initio and DFT calculations were performed at the HF, MP2 and B3LYP levels, employing either full-electron basis sets [3-21G(d) or 6-31G(d)] or an effective core potential with a valence basis set [LanL2DZ(d)]. The best fit to the GED structures was achieved at the MP2 level. Differences between GED and MP2 results for rS-C and angleS-Te-S were explained by the thermal population of excited vibrational states under the experimental conditions. All theoretical models agreed that each compound exists as two stable conformers, one in which the methyl groups are on the same side (g(+)g(-) conformer) and one in which they are on different sides (g(+)g(+) conformer) of the S-Y-S plane (Y = Se, Te). The conformational composition under the experimental conditions could not be resolved from the GED data. Despite GED R-factors and ab initio and DFT energies favouring the g(+)g(+) conformer, it is likely that both conformers are present, for Se(SCH(3))(2) as well as for Te(SCH(3))(2).

  13. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  14. Vibrational frequency analysis, FT-IR, DFT and M06-2X studies on tert-Butyl N-(thiophen-2yl)carbamate

    Science.gov (United States)

    Sert, Yusuf; Singer, L. M.; Findlater, M.; Doğan, Hatice; Çırak, Ç.

    2014-07-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized tert-Butyl N-(thiophen-2yl)carbamate have been investigated. The experimental FT-IR (4000-400 cm-1) spectrum of the molecule in the solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths and bond angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and DFT/M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with the 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The vibrational frequencies have been assigned using potential energy distribution (PED) analysis by using VEDA 4 software. The computational optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data, and with related literature results. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies and the other related molecular energy values have been calculated and are depicted.

  15. Quantitative DFT modeling of product concentration in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study.

    Science.gov (United States)

    Jover, Jesús

    2017-11-08

    DFT calculations are widely used for computing properties, reaction mechanisms and energy profiles in organometallic reactions. A qualitative agreement between the experimental and the calculated results seems to usually be enough to validate a computational methodology but recent advances in computation indicate that a nearly quantitative agreement should be possible if an appropriate DFT study is carried out. Final percent product concentrations, often reported as yields, are by far the most commonly reported properties in experimental metal-mediated synthesis studies but reported DFT studies have not focused on predicting absolute product amounts. The recently reported stoichiometric pentafluoroethylation of benzoic acid chlorides (R-C 6 H 4 COCl) with [(phen)Cu(PPh 3 )C 2 F 5 ] (phen = 1,10-phenanthroline, PPh 3 = triphenylphosphine) has been used as a case study to check whether the experimental product concentrations can be reproduced by any of the most popular DFT approaches with high enough accuracy. To this end, the Gibbs energy profile for the pentafluoroethylation of benzoic acid chloride has been computed using 14 different DFT methods. These computed Gibbs energy profiles have been employed to build kinetic models predicting the final product concentration in solution. The best results are obtained with the D3-dispersion corrected B3LYP functional, which has been successfully used afterwards to model the reaction outcomes of other simple (R = o-Me, p-Me, p-Cl, p-F, etc.) benzoic acid chlorides. The product concentrations of more complex reaction networks in which more than one position of the substrate may be activated by the copper catalyst (R = o-Br and p-I) are also predicted appropriately.

  16. A Theoretical investigation of a potential high energy density compound 3,6,7,8-tetranitro-3,6,7,8-tetraaza-tricyclo[3.1.1.1(2,4]octane

    Directory of Open Access Journals (Sweden)

    Guozheng Zhao

    2013-01-01

    Full Text Available The B3LYP/6-31G (d density functional theory (DFT method was used to study molecular geometry, electronic structure, infrared spectrum (IR and thermodynamic properties. Heat of formation (HOF and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. Thermal stability of 3,6,7,8-tetranitro-3,6,7,8-tetraaza-tricyclo [3.1.1.1(2,4]octane (TTTO was investigated by calculating bond dissociation energy (BDE at the unrestricted B3LYP/6-31G(d level. Results showed the N-NO2 bond is a trigger bond during the thermolysis initiation process. The crystal structure obtained by molecular mechanics (MM methods belongs to P2(1/C space group, with cell parameters a = 8.239 Å, b = 8.079 Å, c = 16.860 Å, Z = 4 and r = 1.922 g cm-3. Both detonation velocity of 9.79 km s-1 and detonation pressure of 44.22 GPa performed similarly to CL-20. According to the quantitative standards of energetics and stability, TTTO essentially satisfies this requirement as a high energy density compound (HEDC.

  17. Vibrational spectroscopic and non-linear optical activity studies on nicotinanilide : A DFT approach

    Science.gov (United States)

    Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

    2015-06-01

    The molecular structure of nicotinanilide was optimized by the DFT/B3LYP method with cc-pVTZ basis set using Gaussian 09 program. The first order hyperpolarizability of the molecule was calculated, which exhibits the higher nonlinear optical activity. The natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction, which leads to the higher nonlinear optical activity of the molecule. The Frontier molecular orbitals analysis of the molecule shows that the delocalization of electron density occurs within the molecule. The lower energy gap indicates that the hydrogen bond formation between the charged species. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program and the corresponding vibrational spectra were simulated. Hence, the nicotinanilide molecule can be a good candidate for second-order NLO material.

  18. Benchmarking fully analytic DFT force fields for vibrational spectroscopy: A study on halogenated compounds

    Science.gov (United States)

    Pietropolli Charmet, Andrea; Cornaton, Yann

    2018-05-01

    This work presents an investigation of the theoretical predictions yielded by anharmonic force fields having the cubic and quartic force constants are computed analytically by means of density functional theory (DFT) using the recursive scheme developed by M. Ringholm et al. (J. Comput. Chem. 35 (2014) 622). Different functionals (namely B3LYP, PBE, PBE0 and PW86x) and basis sets were used for calculating the anharmonic vibrational spectra of two halomethanes. The benchmark analysis carried out demonstrates the reliability and overall good performances offered by hybrid approaches, where the harmonic data obtained at the coupled cluster with single and double excitations level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T), are combined with the fully analytic higher order force constants yielded by DFT functionals. These methods lead to reliable and computationally affordable calculations of anharmonic vibrational spectra with an accuracy comparable to that yielded by hybrid force fields having the anharmonic force fields computed at second order Møller-Plesset perturbation theory (MP2) level of theory using numerical differentiation but without the corresponding potential issues related to computational costs and numerical errors.

  19. Synthesis, spectroscopic and TD-DFT quantum mechanical study of azo-azomethine dyes. A laser induced trans-cis-trans photoisomerization cycle.

    Science.gov (United States)

    Georgiev, Anton; Kostadinov, Anton; Ivanov, Deyan; Dimov, Deyan; Stoyanov, Simeon; Nedelchev, Lian; Nazarova, Dimana; Yancheva, Denitsa

    2018-03-05

    This paper describes the synthesis, spectroscopic characterization and quantum mechanical calculations of three azo-azomethine dyes. The dyes were synthesized via condensation reaction between 4-(dimethylamino)benzaldehyde and three different 4-aminobenzene azo dyes. Quantum chemical calculations on the optimized molecular geometry and electron densities of the trans (E) and cis (Z) isomers and their vibrational frequencies have been computed by using DFT/B3LYP density-functional theory with 6-311++G(d,p) basis set in vacuo. The thermodynamic parameters such as total electronic energy E (RB3LYP), enthalpy H 298 (sum of electronic and thermal enthalpies), free Gibbs energy G 298 (sum of electronic and thermal free Gibbs energies) and dipole moment μ were computed for trans (E) and cis (Z) isomers in order to estimate the ΔE trans→cis , Δμ trans→cis, ΔH trans→cis , ΔG trans→cis and ΔS trans→cis values. After molecular geometry optimization the electronic spectra have been obtained by TD-DFT calculations at same basis set and correlated with the spectra of vapour deposited nanosized films of the dyes. The NBO analysis was performed in order to understand the intramolecular charge transfer and energy of resonance stabilization. Solvatochromism was investigated by UV-VIS spectroscopy in five different organic solvents with increasing polarity. The dynamic photoisomerization experiments have been performed in DMF by pump lasers λ=355nm (mostly E→Z) and λ=491nm (mostly Z→E) in spectral region 300nm - 800nm at equal concentrations and times of illumination in order to investigate the photodynamical trans-cis-trans properties of the CHN and NN chromophore groups of the dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Facile eco-friendly synthesis of 3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-2H-xanthene 1,8(5H,9H)-dione, crystal structure and theoretical study

    Science.gov (United States)

    Tarannum, N.; Singh, M.

    2014-12-01

    New biologically active coumarin derivative, substituted xanthene-dione was synthesized by an easy, facile, cost-effective and efficient method from dimedone and diethylene glycol diacrylate without use of expensive and hazardous catalyst. The synthesis is simple, short, high-yielding and moreover does not require expensive solvents. The compound was characterized by IR, NMR and X-ray crystallography study. DFT (Density Functional Theory) calculations were performed at Becke's three-parameter functional and Lee-Yang-Parr functional (B3LYP) level of calculation and the 6-31G++ basis set was used for ground state geometry optimization. A comparison of the selected bond lengths and bond angles of the crystal structure and theoretically optimized structure by DFT have shown good agreement. The DFT study of electron surface potential (ESP), showed a large intramolecular charge transfer efficiency of the molecule indicating optical activity of xanthene dione.

  1. Thermodynamic DFT analysis of natural gas.

    Science.gov (United States)

    Neto, Abel F G; Huda, Muhammad N; Marques, Francisco C; Borges, Rosivaldo S; Neto, Antonio M J C

    2017-08-01

    Density functional theory was performed for thermodynamic predictions on natural gas, whose B3LYP/6-311++G(d,p), B3LYP/6-31+G(d), CBS-QB3, G3, and G4 methods were applied. Additionally, we carried out thermodynamic predictions using G3/G4 averaged. The calculations were performed for each major component of seven kinds of natural gas and to their respective air + natural gas mixtures at a thermal equilibrium between room temperature and the initial temperature of a combustion chamber during the injection stage. The following thermodynamic properties were obtained: internal energy, enthalpy, Gibbs free energy and entropy, which enabled us to investigate the thermal resistance of fuels. Also, we estimated an important parameter, namely, the specific heat ratio of each natural gas; this allowed us to compare the results with the empirical functions of these parameters, where the B3LYP/6-311++G(d,p) and G3/G4 methods showed better agreements. In addition, relevant information on the thermal and mechanic resistance of natural gases were investigated, as well as the standard thermodynamic properties for the combustion of natural gas. Thus, we show that density functional theory can be useful for predicting the thermodynamic properties of natural gas, enabling the production of more efficient compositions for the investigated fuels. Graphical abstract Investigation of the thermodynamic properties of natural gas through the canonical ensemble model and the density functional theory.

  2. Is HAM/3 (hydrogenic atoms in molecules, version 3 a semiempirical version of dft (density functional theory for ionization processes?

    Directory of Open Access Journals (Sweden)

    Takahata Yuji

    2004-01-01

    Full Text Available We calculated valence-electron vertical ionization potentials (VIPs of nine small molecules, plus uracil and C2F4, by several different methods: semiempirical HAM/3 and AM1 methods, different nonempirical DFT models such as uDI(B88-P86/cc-pVTZ and -epsilon(SAOP/TZP, and ab initio Hartree-Fock (HF /cc-pVTZ. HAM/3 reproduced numerical values more closely to those calculated by the nonempirical DFTs than to those obtained by HF method. Core-electron binding energies (CEBEs of aniline, nitrobenzene and p-nitro aniline, were also calculated by HAM/3 and nonempirical DFT using DE method. A nonempirical DFT model, designated as deltaE KS (PW86-PW91/TZP model, resulted accurate CEBEs (average absolute deviation of 0.14 eV with high efficiency. Although absolute magnitude of HAM/3 CEBEs has error as much as 3 eV, the error in the chemical shifts deltaCEBE is much smaller at 0.55 eV. While the CEBE results do not lead to any definite answer to the question in the title, the trends in valence-electron VIPs indicate that HAM/3 does not approximate DFT with accurate exchange-correlation potentials, but seems to simulate approximate functionals such as B88-P86.

  3. Spectroscopic [FT-IR and FT-Raman] and theoretical [UV-Visible and NMR] analysis on α-Methylstyrene by DFT calculations.

    Science.gov (United States)

    Karthikeyan, N; Joseph Prince, J; Ramalingam, S; Periandy, S

    2015-05-15

    In the present research work, the FT-IR, FT-Raman and (13)C and (1)H NMR spectra of the α-Methylstyrene were recorded. The observed fundamental frequencies in finger print as well as functional group regions were assigned according to their uniqueness region. The Gaussian computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The impact of the presence of vinyl group in phenyl structure of the compound is investigated. The modified vibrational pattern of the molecule associated vinyl group was analyzed. Moreover, (13)C NMR and (1)H NMR were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

  4. Application of gradient-corrected density functional theory to the structures and thermochemistries of ScF3, TiF4, VF5, and CrF6

    International Nuclear Information System (INIS)

    Russo, T.V.; Martin, R.L.; Jeffrey Hay, P.

    1995-01-01

    Density functional theory (DFT) and Hartree--Fock (HF) calculations are reported for the family of transition metal fluorides ScF 3 , TiF 4 , VF 5 , and CrF 6 . Both HF and the local-density approximation (LDA) yield excellent agreement with experimental bond lengths, while the B-LYP gradient-corrected density functional gives bond lengths 0.04-0.05 A too long. An investigation of various combinations of exchange and correlation functionals shows that, for this series, the origin of this behavior lies in the Becke exchange functional. Much improved bond distances are found using the hybrid HF/DFT functional advocated by Becke. This approximation also leads to much improved thermochemistries. The LDA overestimates average bond energies in this series by 30-40 kcal/mol, whereas the B-LYP functional overbinds by only ∼8-12 kcal/mol, and the hybrid HF/DFT method overbinds by only ∼2 kcal/mol. The hybrid method predicts the octahedral isomer of CrF 6 to be more stable than the trigonal prismatic form by 14 kcal/mol. Comparison of theoretical vibrational frequencies with experiment supports the assignment of an octahedral geometry

  5. Synthesis and spectral properties of Methyl-Phenyl pyrazoloquinoxaline fluorescence emitters: Experiment and DFT/TDDFT calculations

    Science.gov (United States)

    Gąsiorski, P.; Matusiewicz, M.; Gondek, E.; Uchacz, T.; Wojtasik, K.; Danel, A.; Shchur, Ya.; Kityk, A. V.

    2018-01-01

    Paper reports the synthesis and spectroscopic studies of two novel 1-Methyl-3-phenyl-1H-pyrazolo[3,4-b]quinoxaline (PQX) derivatives with 6-substituted methyl (MeMPPQX) or methoxy (MeOMPPQX) side groups. The optical absorption and fluorescence emission spectra are recorded in solvents of different polarity. Steady state and time-resolved spectroscopy provide photophysical characterization of MeMPPQX and MeOMPPQX dyes as materials for potential luminescence or electroluminescence applications. Measured optical absorption and fluorescence emission spectra are compared with quantum-chemical DFT/TDDFT calculations using long-range corrected xc-functionals, LRC-BLYP and CAM-B3LYP in combination with self-consistent reaction field model based on linear response (LR), state specific (SS) or corrected linear response (CLR) solvations. Performances of relevant theoretical models and approaches are compared. The reparameterized LRC-BLYP functional (ω = 0.231 Bohr-1) in combination with CLR solvation provides most accurate prediction of both excitation and emission energies. The MeMPPQX and MeOMPPQX dyes represent efficient fluorescence emitters in blue-green region of the visible spectra.

  6. FT-IR, FT-Raman, UV spectra and DFT calculations on monomeric and dimeric structure of 2-amino-5-bromobenzoic acid.

    Science.gov (United States)

    Karabacak, Mehmet; Cinar, Mehmet

    2012-02-01

    In this work, the molecular conformation, vibrational and electronic transition analysis of 2-amino-5-bromobenzoic acid (2A5BrBA) were presented for the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. FT-IR and FT-Raman spectra were recorded in the regions of 400-4000 cm(-1) and 50-4000 cm(-1), respectively. There are four conformers, C1, C2, C3 and C4 for this molecule. The geometrical parameters, energies and wavenumbers have been obtained for all four conformers. The computational results diagnose the most stable conformer of 2A5BrBA as the C1 form. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Raman activities calculated by DFT method have been converted to the corresponding Raman intensities using Raman scattering theory. The UV spectra of investigated compound were recorded in the region of 200-400 nm for ethanol and water solutions. The electronic properties were evaluated with help of time-dependent DFT (TD-DFT) theoretically and results were compared with experimental observations. The thermodynamic properties of the studied compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures. The observed and the calculated geometric parameters, vibrational wavenumbers and electronic transitions were compared with observed data and found to be in good agreement. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Radical scavenging behavior of eriodictyol and fustin flavonoid compounds - A DFT study

    Science.gov (United States)

    Sadasivam, K.; Praveena, R.; Anbakzhakan, K.

    2018-05-01

    The density functional theory (DFT) protocol together with B3LYP/6-311G(d,p) level of theory has been utilized to explore and compare the structural features and molecular characteristics of two naturally occurring flavonoid compounds eriodictyol and fustin. The -OH bond dissociation energy (BDE) for all the radical species have been computed and interpreted in accordance with the radical scavenging activity. The ionization potential (IP) value of fustin flavonoid compound was found to be within the range of synthetic food additives. The polar nature and their capacity to polarise other atoms are established through the dipole moment analysis. Additionally, various parameters that are relevant to chemical potential such as electron affinity, hardness, softness, electro negativity and electrophilic index were calculated and analysed in the light of quercetin flavonoid compound in view of their antioxidant activity. The antioxidant capability of fustin is found to be superior to eriodictyol flavonoid.

  8. Spectroscopic data of Labdane Diterpenes: a theoretical analysis via NMR and DFT; Dados espectroscópicos de diterpenos Labdânicos: uma análise teórica via RMN e DFT

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Fabrine S. de; Silva, Silvana de O.; Alves, Cláudio N.; Guilhon, Giselle M.S.P. [Universidade Federal do Pará (UFPA), Belém, PA (Brazil). Instituto de Ciências Exatas e Naturais; Faria, Lênio J.G. de; Brasil, Davi do S.B., E-mail: davibb@ufpa.br [Universidade Federal do Pará, Belém, PA (Brazil). Instituto de Tecnologia; Muller, Adolfo H. [Centro Universitário do Estado do Pará, Belém, PA (Brazil)

    2015-06-15

    Labdane diterpenes exhibit important bioactivities such as cardiovascular effects in rats as well as effects in the treatment of autoimmune diseases and Alzheimer syndrome. Recently, the labdane diterpenes ent-13-epi-manoil oxide, ribenone and ribenol were isolated from Croton palanostigma. The computational method DFT/B3LYP/cc-pVDZ was used to optimize the structures of these diterpenes and to calculate infrared data. Chemical shifts (δ{sub H} and δ{sub C}) of the minimum energy structures (local minimum) were calculated and compared with the experimental data. Comparison of the NMR data by simple linear regression (SLR) showed satisfactory statistical results with a correlation coefficient (R{sup 2} ) and predictive ability (Q{sup 2}) of over 98%. The predicted NMR data were used to confirm the δ{sub H} values that have not been published. (author)

  9. A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.

    Science.gov (United States)

    Plumley, Joshua A; Dannenberg, J J

    2011-06-01

    We evaluate the performance of ten functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-density functional theory (non-DFT) molecular orbital (MO) calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise (CP) corrected PES. The calculated interaction energies (ΔEs) with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, because of error compensation, the smaller basis sets gave the best results (in comparison to experimental and high-level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. As many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: (1) D95(d,p) with B3LYP, B97D, M06, or MPWB1k; (2) 6-311G(d,p) with B3LYP; (3) D95++(d,p) with B3LYP, B97D, or MPWB1K; (4) 6-311++G(d,p) with B3LYP or B97D; and (5) aug-cc-pVDZ with M05-2X, M06-2X, or X3LYP. Copyright © 2011 Wiley Periodicals, Inc.

  10. In Vitro Antioxidant Activity of Selected 4-Hydroxy-chromene-2-one Derivatives—SAR, QSAR and DFT Studies

    Directory of Open Access Journals (Sweden)

    Slavica Solujić

    2011-04-01

    Full Text Available The series of fifteen synthesized 4-hydroxycoumarin derivatives was subjected to antioxidant activity evaluation in vitro, through total antioxidant capacity, 1,1-diphenyl-2-picryl-hydrazyl (DPPH, hydroxyl radical, lipid peroxide scavenging and chelating activity. The highest activity was detected during the radicals scavenging, with 2b, 6b, 2c, and 4c noticed as the most active. The antioxidant activity was further quantified by the quantitative structure-activity relationships (QSAR studies. For this purpose, the structures were optimized using Paramethric Method 6 (PM6 semi-empirical and Density Functional Theory (DFT B3LYP methods. Bond dissociation enthalpies of coumarin 4-OH, Natural Bond Orbital (NBO gained hybridization of the oxygen, acidity of the hydrogen atom and various molecular descriptors obtained, were correlated with biological activity, after which we designed 20 new antioxidant structures, using the most favorable structural motifs, with much improved predicted activity in vitro.

  11. Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study

    International Nuclear Information System (INIS)

    Tai, Chin-Kuen; Chuang, Wen-Hua; Wang, Bo-Cheng

    2013-01-01

    The DFT/B3LYP/LANL2DZ and TD-DFT calculations have been performed to generate the optimized structures, electronic and photo-physical properties for the porphyrin and zinc(II)–porphyrin (metalloporphyrin) derivatives. The substituted group and side chain effects for these derivatives are discussed in this study. According to the calculation results, the side chain moiety extends the π-delocalization length from the porphyrin core to the side chain moiety. The substituted group with a stronger electron-donating ability increases the energy level of highest occupied molecular orbital (E HOMO ). The side chain moiety with a lower resonance energy decreases E HOMO , the energy level of the lowest unoccupied molecular orbital (E LUMO ), and the energy gap (E g ) between HOMO and LUMO in the porphyrin and zinc(II)–porphyrin derivatives. The natural bonding orbital (NBO) analysis determines the possible electron transfer mechanism from the electron-donating to -withdrawing groups (the side chain moiety) in these porphyrin derivatives. The projected density of state (PDOS) analysis shows that the electron-donating group affects the electron density distribution in both HOMO and LUMO, and the side chain moiety influence the electron density distribution in LUMO. The calculated photo-physical properties (absorption wavelengths and the related oscillator strength, f) in dichloromethane environment for porphyrin and zinc(II)–porphyrin derivatives have been simulated by using the TD-DFT method within the Polarizable Continuum Model (PCM). The present of both of the substituted group and the side chain moiety in these derivatives results in a red shift and broadening of the range of the absorption peaks of the Q/Soret band as compared to porphin. -- Highlights: • Side chain moiety extends the π-delocalization for the porphyrins. • Substituted group increases the energy of highest occupied molecular orbital. • Side chain moiety influences the Q/Soret band of

  12. DFT/TD-DFT characterization of conjugational electronic structures and spectral properties of materials based on thieno[3,2-b][1]benzothiophene for organic photovoltaic and solar cell applications

    Directory of Open Access Journals (Sweden)

    Mohamed Bourass

    2017-07-01

    Full Text Available In this work, a theoretical study on five organic π-conjugated molecules based on thieno[3,2-b][1]benzothiophene using together quantum methods, density functional theory (DFT and its derivative time dependent-density functional theory (TD-DFT is reported. Different electron side groups were introduced as a bridge to investigate their effects on the electronic structure; The HOMO, LUMO, chemical hardness (η, chemical potential (μ, electronegativity (χ, electrophilicity power (ω, reorganization energy total (λtotal, open circuit voltage (Voc, the gap energy and NBO analysis of these compounds have been reported and discussed in this paper. Thus, our aim is to explore their electronic and spectroscopic properties on the basis of the DFT quantum chemical calculations, and at the same time, we are interested to make an idea on the parameters influencing the photovoltaic efficiency toward a better understanding of the structure–property relationships. The calculated results of these compounds reveal that C4, C5, with thiophene and thienopyrazine as a bridge group respectively, can be used as a potential donor of electron in organic Bulk Heterojunction solar cells (BHJ, due to its best electronic and optical properties and good photovoltaic parameters. The study of electronic, optical and structural properties of these compounds could help to design more efficient functional photovoltaic organic materials.

  13. Conformation of the azo bond and its influence on the molecular and crystal structures, IR and Raman spectra, and electron properties of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine - Quantum chemical DFT calculations

    Science.gov (United States)

    Michalski, J.; Bryndal, I.; Lorenc, J.; Hermanowicz, K.; Janczak, J.; Hanuza, J.

    2018-02-01

    The crystal and molecular structures of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine have been determined by X-ray diffraction and quantum chemical DFT calculations. The crystal is monoclinic, space group Cc (No. 9) with Z = 4 with the unit cell parameters: a = 12.083(7), b = 12.881(6), c = 8.134(3) Å and β = 97.09(5)°. The azo-bridge appears in the trans conformation in which C2-N2-N2‧-C1‧ torsion angle takes a value - 178.6(3)°, whereas the dihedral angle between the planes of the phenyl and pyridine rings is 3.5(2)°. The IR and Raman spectra measured in the temperature range 80-350 K and quantum chemical calculations with the use of B3LYP/6-311G(2d,2p) approach confirmed the trans configuration of the azo-bridge as the most stable energetically and allowed determination of the energy other virtual structures. The observed effects were used in the discussion of vibrational dynamics of the studied compound. The energy gap between cis and trans conformers equals to 1.054 eV (0.03873 Hartree). The electron absorption and emission spectra have been measured and analyzed on the basis of DFT calculations. The life time of the excited state is 12 μs and the Stokes shift is close to 5470 cm- 1.

  14. DFT Perspective on the Thermochemistry of Carbon Nitride Synthesis

    KAUST Repository

    Melissen, Sigismund T. A. G.; Steinmann, Stephan N.; Le Bahers, Tangui; Sautet, Philippe

    2016-01-01

    Graphitic (g)-CxNyHz has become a popular family of photoharvesters in photocatalytic water splitting cells, as well as other applications in chemistry. In this Article, different g-CxNyHz structures were studied thermochemically using DFT. Following a benchmark study with different families of functionals, the B3LYP functional was shown to accurately capture the thermochemistry of carbon nitride synthesis. A triple-ζ polarized basis set, in combination with Civalleri’s modification to Grimme’s D2 formalism (with s6 = 0.5) for dispersion interactions, yielded accurate geometries. Grimme’s D3 formalism with Becke–Johnson damping was used to refine the energetic description of dispersion interactions. The stepwise cycloaddition of cyanamide to form melamine was shown to be exergonic, whereas the stepwise deamination of melamine to form g-C3N4 was shown to be endergonic. Of those structures respecting the [C6N9H3]n chemical formula, the structure commonly known as “melon” was found to be most stable, whereas the sp3-hybridized [C6N9H3]n elucidated by Horvath-Bordon et al. was found to be the least stable. Fully polymerized triazine-based g-C3N4 appeared slightly more stable than heptazine-based g-C3N4.

  15. DFT Perspective on the Thermochemistry of Carbon Nitride Synthesis

    KAUST Repository

    Melissen, Sigismund T. A. G.

    2016-10-11

    Graphitic (g)-CxNyHz has become a popular family of photoharvesters in photocatalytic water splitting cells, as well as other applications in chemistry. In this Article, different g-CxNyHz structures were studied thermochemically using DFT. Following a benchmark study with different families of functionals, the B3LYP functional was shown to accurately capture the thermochemistry of carbon nitride synthesis. A triple-ζ polarized basis set, in combination with Civalleri’s modification to Grimme’s D2 formalism (with s6 = 0.5) for dispersion interactions, yielded accurate geometries. Grimme’s D3 formalism with Becke–Johnson damping was used to refine the energetic description of dispersion interactions. The stepwise cycloaddition of cyanamide to form melamine was shown to be exergonic, whereas the stepwise deamination of melamine to form g-C3N4 was shown to be endergonic. Of those structures respecting the [C6N9H3]n chemical formula, the structure commonly known as “melon” was found to be most stable, whereas the sp3-hybridized [C6N9H3]n elucidated by Horvath-Bordon et al. was found to be the least stable. Fully polymerized triazine-based g-C3N4 appeared slightly more stable than heptazine-based g-C3N4.

  16. DADOS ESPECTROSCÓPICOS DE DITERPENOS LABDÂNICOS: UMA ANÁLISE TEÓRICA VIA RMN E DFT

    Directory of Open Access Journals (Sweden)

    Fabrine S. de Souza

    2015-05-01

    Full Text Available Labdane diterpenes exhibit important bioactivities such as cardiovascular effects in rats as well as effects in the treatment of autoimmune diseases and Alzheimer syndrome. Recently, the labdane diterpenes ent-13-epi-manoil oxide, ribenone and ribenol were isolated from Croton palanostigma. The computational method DFT/B3LYP/cc-pVDZ was used to optimize the structures of these diterpenes and to calculate infrared data. Chemical shifts (δH and δC of the minimum energy structures (local minimum were calculated and compared with the experimental data. Comparison of the NMR data by simple linear regression (SLR showed satisfactory statistical results with a correlation coefficient (R2 and predictive ability (Q2 of over 98%. The predicted NMR data were used to confirm the δH values that have not been published.

  17. Alignment of the dye's molecular levels with the TiO2 band edges in dye-sensitized solar cells: a DFT-TDDFT study

    International Nuclear Information System (INIS)

    De Angelis, Filippo; Fantacci, Simona; Selloni, Annabella

    2008-01-01

    We present a theoretical study of the lineup of the LUMO of Ru(II)-polypyridyl (N3 and N719) molecular dyes with the conduction band edge of a TiO 2 anatase nanoparticle. We use density functional theory (DFT) and the Car-Parrinello scheme for efficient optimization of the dye-nanoparticle systems, followed by hybrid B3LYP functional calculations of the electronic structure and time-dependent DFT (TDDFT) determination of the lowest vertical excitation energies. The electronic structure and TDDFT calculations are performed in water solution, using a continuum model. Various approximate procedures to compute the excited state oxidation potential of dye sensitizers are discussed. Our calculations show that the level alignment for the interacting nanoparticle-sensitizer system is very similar, within about 0.1 eV, to that for the separated TiO 2 and dye. The excellent agreement of our results with available experimental data indicates that the approach of this work could be used as an efficient predictive tool to help the optimization of dye-sensitized solar cells.

  18. Synthesis, structural, DFT studies, docking and antibacterial activity of a xanthene based hydrazone ligand

    Science.gov (United States)

    Naseem, Saira; Khalid, Muhammad; Tahir, Muhammad Nawaz; Halim, Mohammad A.; Braga, Ataualpa A. C.; Naseer, Muhammad Moazzam; Shafiq, Zahid

    2017-09-01

    Herein, we present the synthesis of novel xanthene-based hydrazone (1). The chemical structure of 1 was resolved using spectroscopic techniques such as NMR, FT-IR, UV-VIS and X-ray crystallographic approaches. X-ray diffraction analysis shows that the compound (1) crystallizes in triclinic crystal lattice with the Pbar1 space group and diffused to form multi-layered structure due to non-covalent interactions such as intramolecular hydrogen bonding (H.B). In addition to experimental investigation, density functional theory (DFT) calculation with M06-2X/6-31G(d,p) and B3LYP/6-31G(d,p) level of theories was performed on compound (1) to obtain optimized geometry, spectroscopic and electronic properties. DFT optimized geometry shows good agreement with the experimental XRD structure. The hyper conjugative interactions and hydrogen bonding network are responsible for the stability of compound (1) as revealed by natural bond orbital (NBO) calculation. Moreover, hydrogen bonding network in the dimer is confirmed by FT-IR and thermodynamic studies showing excellent agreement with XRD and NBO findings. TD-DFT/UV-VIS analysis provides insight that maximum excitation is found in 1 which shows good agreement with experimental UV-VIS result. The global reactivity parameters are calculated using the energies of frontier molecular orbitals also disclosed that the compound is more stable might be due to hydrogen bonding network. Experimental and molecular docking studies indicated that this compound has anti-bacterial and anti-diabetic properties. The binding affinity of this compound against the multidrug efflux pump subunit AcrB OS=Escherichia coli (strain K12) and Human Pancreatic Alpha-Amylase is -9.2 and -10.00 kcal/mol which are higher than the control drugs. Pi-Pi, Pi-anaion, amide-pi and pi-alkyl bonds play key role in drug-protein complexes.

  19. Synthesis, spectroscopic characterization, DFT studies and antifungal activity of (E)-4-amino-5-[N'-(2-nitro-benzylidene)-hydrazino]-2,4-dihydro-[1,2,4]triazole-3-thione

    Science.gov (United States)

    Joshi, Rachana; Pandey, Nidhi; Yadav, Swatantra Kumar; Tilak, Ragini; Mishra, Hirdyesh; Pokharia, Sandeep

    2018-07-01

    The hydrazino Schiff base (E)-4-amino-5-[N'-(2-nitro-benzylidene)-hydrazino]-2,4-dihydro-[1,2,4]triazole-3-thione was synthesized and structurally characterized by elemental analysis, FT-IR, Raman, 1H and 13C-NMR and UV-Vis studies. A density functional theory (DFT) based electronic structure calculations were accomplished at B3LYP/6-311++G(d,p) level of theory. A comparative analysis of calculated vibrational frequencies with experimental vibrational frequencies was carried out and significant bands were assigned. The results indicate a good correlation (R2 = 0.9974) between experimental and theoretical IR frequencies. The experimental 1H and 13C-NMR resonance signals were also compared to the calculated values. The theoretical UV-Vis spectral studies were carried out using time dependent-DFT method in gas phase and IEFPCM model in solvent field calculation. The geometrical parameters were calculated in the gas phase. Atomic charges at selected atoms were calculated by Mulliken population analysis (MPA), Hirshfeld population analysis (HPA) and Natural population analysis (NPA) schemes. The molecular electrostatic potential (MEP) map was calculated to assign reactive site on the surface of the molecule. The conceptual-DFT based global and local reactivity descriptors were calculated to obtain an insight into the reactivity behaviour. The frontier molecular orbital analysis was carried out to study the charge transfer within the molecule. The detailed natural bond orbital (NBO) analysis was performed to obtain an insight into the intramolecular conjugative electronic interactions. The titled compound was screened for in vitro antifungal activity against four fungal strains and the results obtained are explained through in silico molecular docking studies.

  20. Studies on the first-order hyperpolarizability and terahertz generation in 3-nitroaniline

    International Nuclear Information System (INIS)

    Krishnakumar, V.; Nagalakshmi, R.

    2008-01-01

    Single crystals of 3-nitroaniline (C 6 H 6 N 2 O 2 ) also called as m-nitroaniline (m-NA) have been grown by adopting slow evaporation solution growth technique at room temperature using methanol as a solvent. To reveal the microscopic nonlinear optical properties, the first-order hyperpolarizability (β) was evaluated by using the density functional theory (DFT) quantum chemical calculations at B3LYP/3-21 G (d,p) level. According to the results of DFT calculations, the grown crystals exhibit non-zero β values and it might have microscopic nonlinear optical behavior which is seven times more than that of urea. Terahertz (1 THz=10 12 Hz) radiation was also generated in the title organic nonlinear optical crystal using ultra short femtosecond laser

  1. Variable-temperature NMR and conformational analysis of Oenothein B

    International Nuclear Information System (INIS)

    Santos, Suzana C.; Carvalho, Ariadne G.; Fortes, Gilmara A.C.; Ferri, Pedro H.; Oliveira, Anselmo E. de

    2014-01-01

    Oenothein B is a dimeric hydrolyzable tannin with a wide range of biological activities, such as antitumour, anti-inflammatory and antiviral. Its nuclear magnetic resonance (NMR) at room temperature show duplications and broadening of signals. Experiments of 1D and 2D NMR at lower temperatures were useful for the complete NMR assignments of all hydrogens and carbons. The 3D structure of the most stable conformer was determined for the first time by nuclear Overhauser effect spectroscopy (NOESY) experiment (-20 deg C) and density functional theory (DFT)(B3LYP/6-31G)/ polarizable continuum model (PCM) quantum chemical calculations. The favoured conformation showed a highly compacted geometry and a lack of symmetry, in which the two valoneoyl groups showed distinct conformational parameters and stabilities. (author)

  2. Variable-temperature NMR and conformational analysis of Oenothein B

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Suzana C.; Carvalho, Ariadne G.; Fortes, Gilmara A.C.; Ferri, Pedro H.; Oliveira, Anselmo E. de, [Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de Quimica

    2014-02-15

    Oenothein B is a dimeric hydrolyzable tannin with a wide range of biological activities, such as antitumour, anti-inflammatory and antiviral. Its nuclear magnetic resonance (NMR) at room temperature show duplications and broadening of signals. Experiments of 1D and 2D NMR at lower temperatures were useful for the complete NMR assignments of all hydrogens and carbons. The 3D structure of the most stable conformer was determined for the first time by nuclear Overhauser effect spectroscopy (NOESY) experiment (-20 deg C) and density functional theory (DFT)(B3LYP/6-31G)/ polarizable continuum model (PCM) quantum chemical calculations. The favoured conformation showed a highly compacted geometry and a lack of symmetry, in which the two valoneoyl groups showed distinct conformational parameters and stabilities. (author)

  3. Experimental and theoretical studies of (FT-IR, FT-Raman, UV-Visible and DFT) 4-(6-methoxynaphthalen-2-yl) butan-2-one.

    Science.gov (United States)

    Govindasamy, P; Gunasekaran, S

    2015-01-01

    In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-50 cm(-1) and 4000-450 cm(-1) respectively for 4-(6-methoxynaphthalen-2-yl) butan-2-one (abbreviated as 4MNBO) molecule. Theoretical calculations were performed by density functional theory (DFT/B3LYP) method using 6-311G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and calculated wavenumber value of most of the fundamentals were very small. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The UV-Vis spectrum was recorded in the methanol solution. The energy, wavelength and oscillator's strength were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Thermodynamic properties of 4MNBO at different temperature have been calculated. The molecular electrostatic potential surface (MESP) and Frontier molecular orbital's (FMO's) analysis were investigated using theoretical calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. A DFT study on the deprotonation antioxidant mechanistic step of ortho-substituted phenolic cation radicals

    International Nuclear Information System (INIS)

    Vafiadis, Anastasios P.; Bakalbassis, Evangelos G.

    2005-01-01

    The conformers of the 2-, 3- and 4-substituted phenolic cation radicals, 2-X-, 3-X- and 4-X-ArOH ·+ , and the respective phenoxyl radicals, ArO · , the intramolecular hydrogen bond strength (ΔH intra ) estimate along with the electronic effects of five electron withdrawing (EWG) and eight electron donating groups (EDG) on the gas-phase O-H proton dissociation enthalpies, (PDEs), of the short-lived, 2-X-ArOH ·+ , (involved in the single-electron transfer antioxidant mechanism), are studied at the DFT/B3LYP level of theory. EWG result to smaller PDEs, hence to stronger acidity; EDG to weaker acidity. The deprotonation antioxidant mechanistic step is not a rate-controlling step for 2-X-ArOH to scavenge free radicals. Approximate estimations of the ΔPDEs (hence acidities as well) can be derived from calculated structural and/or vibrational frequency values. ΔH intra s correlate reasonably with geometrical parameters for the closed-shell, neutral counterparts, in contrast with previous estimates

  5. The DFT investigations of the electron injection in hydrazone-based sensitizers

    KAUST Repository

    Al-Sehemi, Abdullah G.

    2012-03-01

    Quantum chemical calculations were carried out by using density functional theory and time-dependant density functional theory at B3LYP/6-31G(d) and TD-B3LYP/6-31G(d) level of theories. The absorption spectra have been computed with and without solvent. The calculated absorption spectra in ethanol, acetonitrile, and methanol are in good agreement with experimental evidences. The absorption spectra are red shifted compared to System1. On the basis of electron injection and electronic coupling constant, we have shed light on the nature of different sensitizers. The coplanarity between the benzene near anchoring group having LUMO and the bridge (N-N) is broken in System6 and System7 that would hamper the recombination process. The electron injection of System2-System10 is superior to System1. The highest electronic coupling constant has been observed for System6 that followed the System7 and System8. The light-harvesting efficiency of all the sensitizers enlarged in acetonitrile and ethanol. The long-range-corrected functional (LC-BLYP), Coulomb-attenuating method (CAM-B3LYP), and BH and HLYP functional underestimate the excitation energies while B3LYP is good to reproduce the experimental data. Moreover, we have investigated the effect of cyanoacetic acid as anchoring group on the electron injection. © 2012 Springer-Verlag.

  6. Theoretical Characteristics of Metalloporphyrins (OEP) M (CH 3 ) (M=Al, Ga, In and Tl)

    OpenAIRE

    Lepetit , M.B.; Kabbaj , O.K.; Zrineh , A.

    2017-01-01

    International audience; A theoretical study of metalloporphyrins molecules (OEP) M (CH 3) (M=Al, Ga, In and Tl) are brought to a few experimental data and to give background for future development of these complexes. The Quantum Chemistry Program (ORCA) program package based on Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TDDFT) for transitions at the B3LYP level with ANO 2ζ+P base was used for calculations and determination of structural properties, electroni...

  7. Vibrational, DFT, and thermal analysis of 2,4,6-triamino-1,3,5-triazin-1-ium 3-(prop-2-enoyloxy) propanoate acrylic acid monosolvate monohydrate

    Science.gov (United States)

    Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Anbalagan, G.

    2013-12-01

    New organic crystals of 2,4,6-triamino-1,3,5-triazin-1-ium 3-(prop-2-enoyloxy) propanoate acrylic acid monosolvate monohydrate (MAC) have been obtained from aqueous solution by the slow solvent evaporation method at room temperature. Single crystal X-ray diffraction analysis reveals that the compound crystallises in the triclinic system with centrosymmetric space group P-1. FT-IR and FT-Raman spectra of MAC have been recorded and analyzed. The molecular geometry and vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimization based on density functional theory (DFT) B3LYP method with 6-31G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction data. The theoretical results show that the optimized geometry can well reproduce the crystal structure, and the calculated vibrational frequency values show good agreement with experimental values. A study of the electronic properties, such as HOMO and LUMO energies and Molecular electrostatic potential (MEP) were performed. Mulliken charges and NBO charges of the title molecule were also calculated and interpreted. Thermogravimetric analysis has been done to study the thermal behaviour of MAC. The 13C and 1H nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

  8. Compton profiles and Mulliken’s populations of cobalt, nickel and copper tungstates: Experiment and theory

    Energy Technology Data Exchange (ETDEWEB)

    Meena, B.S. [Department of Physics, M.L. Sukhadia University, Udaipur 313001, Rajasthan (India); Heda, N.L. [Department of Pure and Applied Physics, University of Kota, Kota 324010, Rajasthan (India); Kumar, Kishor; Bhatt, Samir; Mund, H.S. [Department of Physics, M.L. Sukhadia University, Udaipur 313001, Rajasthan (India); Ahuja, B.L., E-mail: blahuja@yahoo.com [Department of Physics, M.L. Sukhadia University, Udaipur 313001, Rajasthan (India)

    2016-03-01

    We present the first ever studies on Compton profiles of AWO{sub 4} (A=Co, Ni and Cu) using 661.65 keV γ-rays emitted by {sup 137}Cs source. The experimental momentum densities have been employed to validate exchange and correlation potentials within linear combination of atomic orbitals (LCAO) method. Density functional theory (DFT) with local density approximation and generalized gradient approximation and also the hybridization of Hartree-Fock and DFT (B3LYP and PBE0) have been considered under LCAO scheme. The LCAO-B3LYP scheme is found to be in better agreement with the experimental data than other approximations considered in this work, suggesting applicability of B3LYP approach in predicting the electronic properties of these tungstates. The Mulliken’s population (MP) data show charge transfer from Co/Ni/Cu and W to O atoms. The experimental profiles when normalized to same area show almost similar localization of 3d electrons (in real space) of Ni and Cu which is lower than that of Co in their AWO{sub 4} environment.

  9. Electronic structure and magnetism of new ilmenite compounds for spintronic devices: FeBO{sub 3} (B = Ti, Hf, Zr, Si, Ge, Sn)

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, R.A.P. [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Camilo, A. [Department of Physics, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Lazaro, S.R. de, E-mail: srlazaro@uepg.br [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil)

    2015-11-15

    First-principles calculations were performed in the framework of Density Functional Theory (DFT) within hybrid functional (B3LYP) to study the electronic structure and magnetic properties of new ilmenite FeBO{sub 3} (B=Ti, Hf, Zr, Si, Ge, Sn) materials. In particular, the magnetic exchange interaction between Fe{sup 2+} layers is dependent on the interlayer distance and it can be controlled by ionic radius of B-site cation. Thus, Fe(Ti, Si, Ge)O{sub 3} are antiferromagnetic materials, while Fe(Zr, Hf, Sn)O{sub 3} are ferromagnetic. We also argue that antiferromagnetic materials and FeZrO{sub 3} are convectional semiconductors, whereas FeHfO{sub 3} and FeSnO{sub 3} exhibit intrinsic half-metallic behavior, making them promising candidates for spintronic devices. - Highlights: • We study electronic structure and magnetism of new FeBO{sub 3} (B=Ti, Hf, Zr, Si, Ge, Sn) ilmenite materials. • We found that magnetic ordering of Fe-based ilmenite materials can be controlled by size of B-site cation. • Fe(Ti, Zr, Si, Ge)O{sub 3} are convectional semiconductors. • FeHfO{sub 3} and FeSnO{sub 3} exhibit intrinsic half-metallic behavior with potential application for spintronic devices.

  10. Simulation of circularly polarized luminescence spectra using coupled cluster theory

    Energy Technology Data Exchange (ETDEWEB)

    McAlexander, Harley R.; Crawford, T. Daniel, E-mail: crawdad@vt.edu [Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061 (United States)

    2015-04-21

    We report the first computations of circularly polarized luminescence (CPL) rotatory strengths at the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) level of theory. Using a test set of eight chiral ketones, we compare both dipole and rotatory strengths for absorption (electronic circular dichroism) and emission to the results from time-dependent density-functional theory (TD-DFT) and available experimental data for both valence and Rydberg transitions. For two of the compounds, we obtained optimized geometries of the lowest several excited states using both EOM-CCSD and TD-DFT and determined that structures and EOM-CCSD transition properties obtained with each structure were sufficiently similar that TD-DFT optimizations were acceptable for the remaining test cases. Agreement between EOM-CCSD and the Becke three-parameter exchange function and Lee-Yang-Parr correlation functional (B3LYP) corrected using the Coulomb attenuating method (CAM-B3LYP) is typically good for most of the transitions, though agreement with the uncorrected B3LYP functional is significantly worse for all reported properties. The choice of length vs. velocity representation of the electric dipole operator has little impact on the EOM-CCSD transition strengths for nearly all of the states we examined. For a pair of closely related β, γ-enones, (1R)-7-methylenebicyclo[2.2.1]heptan-2-one and (1S)-2-methylenebicyclo[2.2.1]heptan-7-one, we find that EOM-CCSD and CAM-B3LYP agree with the energetic ordering of the two possible excited-state conformations, resulting in good agreement with experimental rotatory strengths in both absorption and emission, whereas B3LYP yields a qualitatively incorrect result for the CPL signal of (1S)-2-methylenebicyclo[2.2.1]heptan-7-one. Finally, we predict that one of the compounds considered here, trans-bicyclo[3.3.0]octane-3,7-dione, is unique in that it exhibits an achiral ground state and a chiral first excited state, leading to a strong CPL

  11. A multi-level quantum mechanics and molecular mechanics study of SN2 reaction at nitrogen: NH2Cl + OH(-) in aqueous solution.

    Science.gov (United States)

    Lv, Jing; Zhang, Jingxue; Wang, Dunyou

    2016-02-17

    We employed a multi-level quantum mechanics and molecular mechanics approach to study the reaction NH2Cl + OH(-) in aqueous solution. The multi-level quantum method (including the DFT method with both the B3LYP and M06-2X exchange-correlation functionals and the CCSD(T) method, and both methods with the aug-cc-pVDZ basis set) was used to treat the quantum reaction region in different stages of the calculation in order to obtain an accurate potential of mean force. The obtained free energy activation barriers at the DFT/MM level of theory yielded a big difference of 21.8 kcal mol(-1) with the B3LYP functional and 27.4 kcal mol(-1) with the M06-2X functional respectively. Nonetheless, the barrier heights become very close when shifted from DFT to CCSD(T): 22.4 kcal mol(-1) and 22.9 kcal mol(-1) at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM levels of theory, respectively. The free reaction energy obtained using CCSD(T)(M06-2X)/MM shows an excellent agreement with the one calculated using the available gas-phase data. Aqueous solution plays a significant role in shaping the reaction profile. In total, the water solution contributes 13.3 kcal mol(-1) and 14.6 kcal mol(-1) to the free energy barrier heights at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM respectively. The title reaction at nitrogen is a faster reaction than the corresponding reaction at carbon, CH3Cl + OH(-).

  12. De(side chain) model of epothilone: bioconformer interconversions DFT study.

    Science.gov (United States)

    Rusinska-Roszak, Danuta; Lozynski, Marek

    2009-07-01

    Using ab initio methods, we have studied conformations of the de(sidechain)de(dioxy)difluoroepothilone model to quantify the effect of stability change between the exo and endo conformers of the epoxy ring. The DFT minimization of the macrolactone ring reveals four low energy conformers, although MP2 predicted five stable structures. The model tested with DFT hybride functional (B3LYP/6-31+G(d,p)) exhibits the global minimum for one of the exo forms (C), experimentally observed in the solid state, but unexpectedly with the MP2 electron correlation method for the virtual endo form (W). Using the QST3 technique, several pathways were found for the conversion of the low energy conformers to the other low energy exo representatives, as well as within the endo analog subset. The potential energy relationships obtained for several exo forms suggest a high conformational mobility between three, experimentally observed, conformers. The high rotational barrier, however, excludes direct equilibrium with experimental EC-derived endo form S. The highest calculated transition state for the conversion of the most stable exo M interligand to the endo S form is approximately a 28 kcal/mol above the energy of the former. The two-step interconversion of the exo H conformer to the endo S requires at least 28 kcal/mol. Surprisingly, we found that the transition state energy of the H form to the virtual endo W has the acceptable value of about 9 kcal/mol and the next energy barrier for free interconversion of endo W to endo S is 13 kcal/mol.

  13. The autoimmunity risk variant LYP-W620 cooperates with CSK in the regulation of TCR signaling.

    Directory of Open Access Journals (Sweden)

    María Luisa de la Puerta

    Full Text Available The protein tyrosine phosphatase LYP, a key regulator of TCR signaling, presents a single nucleotide polymorphism, C1858T, associated with several autoimmune diseases such as type I diabetes, rheumatoid arthritis, and lupus. This polymorphism changes an R by a W in the P1 Pro rich motif of LYP, which binds to CSK SH3 domain, another negative regulator of TCR signaling. Based on the analysis of the mouse homologue, Pep, it was proposed that LYP and CSK bind constitutively to inhibit LCK and subsequently TCR signaling. The detailed study of LYP/CSK interaction, here presented, showed that LYP/CSK interaction was inducible upon TCR stimulation, and involved LYP P1 and P2 motifs, and CSK SH3 and SH2 domains. Abrogating LYP/CSK interaction did not preclude the regulation of TCR signaling by these proteins.

  14. Characterization of prepared In2O3 thin films: The FT-IR, FT-Raman, UV-Visible investigation and optical analysis.

    Science.gov (United States)

    Panneerdoss, I Joseph; Jeyakumar, S Johnson; Ramalingam, S; Jothibas, M

    2015-08-05

    In this original work, the Indium oxide (In2O3) thin film is deposited cleanly on microscope glass substrate at different temperatures by spray pyrolysis technique. The physical properties of the films are characterized by XRD, SEM, AFM and AFM measurements. The spectroscopic investigation has been carried out on the results of FT-IR, FT-Raman and UV-Visible. XRD analysis exposed that the structural transformation of films from stoichiometric to non-stoichiometric orientation of the plane vice versa and also found that, the film is polycrystalline in nature having cubic crystal structure with a preferred grain orientation along (222) plane. SEM and AFM studies revealed that, the film with 0.1M at 500°C has spherical grains with uniform dimension. The complete vibrational analysis has been carried out and the optimized parameters are calculated using HF and DFT (CAM-B3LYP, B3LYP and B3PW91) methods with 3-21G(d,p) basis set. Furthermore, NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) technique. The molecular electronic properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, molecular electrostatic potential energy (MEP) analysis and Polarizability first order hyperpolarizability calculations are performed by time dependent DFT (TD-DFT) approach. The energy excitation on electronic structure is investigated and the assignment of the absorption bands in the electronic spectra of steady compound is discussed. The calculated HOMO and LUMO energies showed the enhancement of energy gap by the addition of substitutions with the base molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) at different temperatures are calculated and interpreted in gas phase. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

  15. 2-Oxo-2H-chromen-3-yl benzoate

    Directory of Open Access Journals (Sweden)

    Konan René Kambo

    2017-05-01

    Full Text Available In the title compound, C16H10O4, the dihedral angle between the coumarin ring system (r.m.s. deviation = 0.015 Å and the benzoate group is 83.58 (9°, which compares to a value of 81.8° obtained from a DFT calculation at the B3LYP/6–311 G(d,p level. In the crystal, C—O...π and C—H...π interactions and aromatic π–π [Cg...Cg = 3.7214 (14 and 3.7059 (14 Å] stacking generate a three-dimensional network.

  16. Synthesis, structural, spectroscopic, anti-cancer and molecular docking studies on novel 2-[(Anthracene-9-ylmethylene)amino]-2-methylpropane-1,3-diol using XRD, FTIR, NMR, UV-Vis spectra and DFT

    Science.gov (United States)

    Pavitha, P.; Prashanth, J.; Ramu, G.; Ramesh, G.; Mamatha, K.; Venkatram Reddy, Byru

    2017-11-01

    The novel titled compound 2-[(Anthracene-9-ylmethylene)amino]-2-methylpropane-1,3-diol (AMD) has been synthesized by slow evaporation technique from mixed solvent system of methanol with anthracene-9-carbaldehyde and 2-amino-2-methylpropane-1,3-diol. The synthesized molecule AMD was characterized experimentally by single crystal XRD, FTIR, NMR and UV-Vis spectra and density functional theory (DFT) computations. The structure of the crystal has been determined as orthorhombic system with space group P 21 21 21 and the cell parameters are obtained using XRD data. The optimized ground state geometry of the molecule is determined by evaluating torsional potentials as a function of angle of free rotation around Csbnd C bonds of functional groups by DFT method employing B3LYP functional with 6-311++G(d,p) basis set. All the fundamental vibrations of the molecule are assigned unambiguously using potential energy distribution (PED) obtained in the DFT computations. The rms error between the observed and scaled frequencies is 6.20 cm-1. The values of dipole moment, polarizability and hyperpolarizability are evaluated to study the NLO behavior of the molecule. The HOMO-LUMO energies and thermodynamic parameters are also determined. The molecular electrostatic surface potential (MESP) is mapped to obtain the charge density distribution. The 1H and 13C NMR chemical shifts of the molecule are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. UV-visible spectrum of the compound is also recorded in the region 200-800 nm to know the type of electronic transitions involved. The anti-cancer activity of AMD is determined against human breast cancer cell line MCF-7 and human prostate cancer cell line PC-3 and correlated the results with study of molecular docking against pharmacological protein IDO-1 receptor.

  17. A DFT study on the mechanisms for the cycloaddition reactions between 1-aza-2-azoniaallene cations and acetylenes.

    Science.gov (United States)

    Wang, Jing-mei; Li, Zhi-ming; Wang, Quan-rui; Tao, Feng-gang

    2013-01-01

    The mechanisms of cycloaddition reactions between 1-aza-2-azoniaallene cations 1 and acetylenes 2 have been investigated using the global electrophilicity and nucleophilicity of the corresponding reactants as global reactivity indexes defined within the conceptual density functional theory. The reactivity and regioselectivity of these reactions were predicted by analysis of the energies, geometries, and electronic nature of the transition state structures. The theoretical results revealed that the reaction features a tandem process: an ionic 1,3-dipolar cycloaddition to produce the cycloadducts 3 H-pyrazolium salts 3 followed by a [1,2]-shift affording the thermodynamically more stable adducts 4 or 5. The mechanism of the cycloaddition reactions can be described as an asynchronous concerted pathway with reverse electron demand. The model reaction has also been investigated at the QCISD/6-31++G(d,p) and CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) levels as well as by the DFT. The polarizable continuum model, at the B3LYP/6-31++G(d,p) level of theory, was used to study solvent effects on all the studied reactions. In solvent dichloromethane, all the initial cycloadducts 3 were obtained via direct ionic process as the result of the solvent effect. The consecutive [1,2]-shift reaction, in which intermediates 3 are rearranged to the five-membered heterocycles 4/5, is proved to be a kinetically controlled reaction, and the regioselectivity can be modulated by varying the migrant. The LOL function and RDG function based on localized electron analysis were used to analysis the covalent bond and noncovalent interactions in order to unravel the mechanism of the title reactions.

  18. Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

    Science.gov (United States)

    Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

    2017-11-01

    Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

  19. Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self- consistent field wave functions

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Jensen, Hans Jørgen Aagaard; Knecht, Stefan

    2013-01-01

    -MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the CAM-B3LYP functional. The SOPPA-srDFT scheme is tested for a subset of molecules used for benchmarking...

  20. Experimental FT-IR, Laser-Raman and DFT spectroscopic analysis of a potential chemotherapeutic agent 6-(2-methylpropyl)-4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carbonitrile.

    Science.gov (United States)

    Sert, Yusuf; Al-Turkistani, Abdulghafoor A; Al-Deeb, Omar A; El-Emam, Ali A; Ucun, Fatih; Çırak, Çağrı

    2014-01-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized potential chemotherapeutic agent namely, 6-(2-methylpropyl)-4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carbonitrile have been investigated. The experimental FT-IR (4000-400 cm(-1)) and Laser-Raman spectra (4000-100 cm(-1)) of the molecule in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths and bond angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with 6-311++G(d,p) basis set by Gaussian 09 W software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis by using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data, and with the results in the literature. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies and the other related molecular energy values have been calculated and depicted. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Quantum chemical study, spectroscopic investigations, NBO and HOMO-LUMO analyses of 3-aminoquinoline (3AQ) and [Ag(3AQ)2(TCA)] complex (TCA = Trichloroacetate)

    Science.gov (United States)

    Soliman, Saied M.; Kassem, Taher S.; Badr, Ahmed M. A.; Abu Youssef, Morsy A.; Assem, Rania

    2014-09-01

    The new [Ag(3AQ)2(TCA)]; (3AQ = 3-aminoquinoline and TCA = Trichloroacetate) complex is synthesized and characterized using elemental analysis, FTIR, NMR and mass spectroscopy. The molecular geometry, vibrational frequencies, gauge-including atomic orbital (GIAO) 1H chemical shift values of the free and coordinated 3AQ in the ground state have been calculated by using DFT/B3LYP method. The TD-DFT results of the [Ag(3AQ)2(TCA)] complex showed a π-π* transition band at 240.3-242.6 nm (f = 0.1334-0.1348) which has longer wavelength and lower absorption intensity than that for the free 3AQ (233.2 nm, f = 0.3958). Dipole moment, polarizability and HOMO-LUMO gap values predicted better nonlinear optical properties (NLO) for the [Ag(3AQ)2(TCA)] than the 3AQ ligand. NBO analysis has been used to predict the most accurate Lewis structure of the studied molecules. The energies of the different intramolecular charge transfer (ICT) interactions within the studied molecules were estimated using second order perturbation theory.

  2. Synthesis, spectroscopic characterization, theoretical study and anti-hepatic cancer activity study of 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate, a novel curcumin congener

    Science.gov (United States)

    Srivastava, Sangeeta; Gupta, Preeti; Singh, Ranvijay Pratap; Jafri, Asif; Arshad, M.; Banerjee, Monisha

    2017-08-01

    In the present work 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate (2), a novel curcumin ester was synthesized. The molecular structure and spectroscopic analysis were performed using experimental techniques like FT-IR, 1H,13C NMR, mass and UV-visible as well as theoretical calculations. The theoretical calculations were done by DFT level of theory using B3LYP/6-31G (d,p) basis set. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). The electronic properties such as frontier orbitals and band gap energies have been calculated using time dependent density functional theory (TD-DFT). The strength and nature of weak intramolecular interactions have been studied by AIM approach. Global and local reactivity descriptors have been computed to predict reactivity and reactive sites in the molecule. First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out. The anti-hepatic cancer activity of compound 2 was also carried out.

  3. Antioxidant behavior of mearnsetin and myricetin flavonoid compounds — A DFT study

    Science.gov (United States)

    Sadasivam, K.; Kumaresan, R.

    2011-06-01

    The molecular characteristics of two naturally occurring flavonoid compounds mearnsetin and myricetin have been computed using density functional theory (DFT) approach with B3LYP/6-311G(d,p) level of theory. The computation and analysis of bond dissociation enthalpy magnitudes for all the OH sites for both the compounds clearly denotes the contribution of the B-ring for the antioxidant activity. The analysis has also indicated the higher values of BDE on the C5-OH radical species in both the compounds. The computed vibrational frequency analysis indicates the absence of imaginary frequency in the neutral as well as radical species of both the flavonoid compounds. The ionisation potential (IP) analysis was found to be within the range of the IP of synthetic food additives. In addition, various molecular descriptors such as electron affinity, hardness, softness, electronegativity, electrophilic index have also been calculated and the validity of Koopman's theorem is verified. The plot of frontier molecular orbital and spin density distribution analysis for neutral and the corresponding radical species for both the compounds have been computed and interpreted. The polar nature and their polarizing capacity are well established through the analysis of dipole moment and polarisability magnitudes.

  4. Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Atsushi; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture 2500 Hassaka, Hikone, Shiga, 522-8533 (Japan)

    2016-02-01

    Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

  5. Substituent influence on the structural, vibrational and electronic properties of 2,5-dihydrothiophene-1,1-dioxide by experimental and DFT methods.

    Science.gov (United States)

    Arjunan, V; Thirunarayanan, S; Durga Devi, G; Mohan, S

    2015-11-05

    Spectroscopic and theoretical quantum chemical studies of 2,5-dihydrothiophene-1,1-dioxide and 3-methyl-2,5-dihydrothiophene-1,1-dioxide have been carried out by FTIR and FT-Raman spectral techniques along with B3LYP methods. The geometry of the compounds have been optimised by B3LYP method with 6-311++G(∗∗) and cc-pVTZ basis sets. The geometrical parameters obtained at B3LYP levels have been compared with the experimental values. Molecular electrostatic potential surface, total electron density distribution and frontier molecular orbital are constructed at B3LYP/cc-pVTZ level to understand the electronic properties. The charge density distribution and sites of chemical reactivity of the molecules have been obtained by mapping electron density isosurface with electrostatic potential surfaces. Natural bond orbital analysis of the molecules are carried out and the occupancies and the atomic hybrid contributions are calculated. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Interactions between alkaline earth cations and oxo ligands. DFT study of the affinity of the Mg²+ cation for phosphoryl ligands.

    Science.gov (United States)

    da Costa, Leonardo Moreira; de Mesquita Carneiro, José Walkimar; Paes, Lilian Weitzel Coelho

    2011-08-01

    DFT (B3LYP/6-31+G(d)) calculations of Mg(2+) affinities for a set of phosphoryl ligands were performed. Two types of ligands were studied: a set of trivalent [O = P(R)] and a set of pentavalent phosphoryl ligands [O = P(R)(3)] (R = H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either bound directly to the phosphorus atom or to the para position of a phenyl ring. The affinity of the Mg(2+) cation for the ligands was quantified by means of the enthalpy for the substitution of one water molecule in the [Mg(H(2)O)(6)](2+) complex for a ligand. The enthalpy of substitution was correlated with electronic and geometric parameters. Electron-donor groups increase the interaction between the cation and the ligand, while electron-acceptor groups decrease the interaction enthalpy.

  7. Hartree-Fock (HF) method and density functional theory calculations of Methanol to Gasoline (MTG) reaction

    International Nuclear Information System (INIS)

    Seddigi, Z.S.

    2004-01-01

    We found interesting results regarding some thermodynamical parameters (Delta H, Delta G and Delta S of the MTG Reaction and FTIR Spectra of methanol and dimethylether, using the Hartree-Fock method and Density Functional Theory (DFT) calculations at different computational levels. It is the aim of this paper to highlight these results. The GAUSSIAN 98 program was used to carry out the LCAO-MO-SCF calculations at the following levels: RHF/3-21g, RHF/6-31g and DFT/B3LYP/d95**. Calculations at the restricted Hartree-Fock levels (FHR/3-22 g and RHF/6-31g) were performed since they are expensive as other levels (DFT/B3LYP/d95**. In case of the HF method, working with larger basis set (6-31g) has improved the values slightly, which is as expected. We have noticed that performing calculations at higher levels (DFT/B3LY/D95**) than the Hartree-Fock method does not dramatically improve the situation. Indeed RHF is a reasonable approximation for many single gas phase molecular calculations. HF calculations at relatively small basis sets are adequate. The theoretical vibrational spectra of both methanol and dimethylether were compared with experimental results. (author)

  8. First principles DFT study of dye-sensitized CdS quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Kalpna; Singh, Kh. S. [Department of Physics, D. J. College, Baraut -250611, U.P. (India); Kishor, Shyam, E-mail: shyam387@gmail.com [Department of Chemistry, J. V. College, Baraut -250611, U.P. (India); Josefesson, Ida; Odelius, Michael [Fysikum, Albanova University Center, Stockholm University, S-106 91 Stockholm (Sweden); Ramaniah, Lavanya M. [High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Mumbai-400085 (India)

    2014-04-24

    Dye-sensitized quantum dots (QDs) are considered promising candidates for dye-sensitized solar cells. In order to maximize their efficiency, detailed theoretical studies are important. Here, we report a first principles density functional theory (DFT) investigation of experimentally realized dye - sensitized QD / ligand systems, viz., Cd{sub 16}S{sub 16}, capped with acetate molecules and a coumarin dye. The hybrid B3LYP functional and a 6−311+G(d,p)/LANL2dz basis set are used to study the geometric, energetic and electronic properties of these clusters. There is significant structural rearrangement in all the clusters studied - on the surface for the bare QD, and in the positions of the acetate / dye ligands for the ligated QDs. The density of states (DOS) of the bare QD shows states in the band gap, which disappear on surface passivation with the acetate molecules. Interestingly, in the dye-sensitised QD, the HOMO is found to be localized mainly on the dye molecule, while the LUMO is on the QD, as required for photo-induced electron injection from the dye to the QD.

  9. TD-DFT Investigation of the Magnetic Circular Dichroism Spectra of Some Purine and Pyrimidine Bases of Nucleic Acids

    DEFF Research Database (Denmark)

    Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick

    2015-01-01

    We present a computational study of the magnetic circular dichroism (MCD) spectra in the 200–300 nm wavelength region of purine and its derivative hypoxanthine, as well as of the pyrimidine bases of nucleic acids uracil, thymine, and cytosine, using the B3LYP and CAM–B3LYP functionals. Solvent...

  10. Phase transition and intramolecular hydrogen bonding in nitro derivatives of ortho-hydroxy acetophenones

    Science.gov (United States)

    Filarowski, A.; Kochel, A.; Koll, A.; Bator, G.; Mukherjee, S.

    2006-03-01

    The crystal structures of two ortho-hydroxy aryl ketones (5-chloro-3-nitro-2-hydroxyacetophenone, 5-methyl-3-nitro-2-hydroxyacetophenone and the complex 5-chloro-3-nitro-2-hydroxyacetophenone with 2-aminobenzoic acid (anthranilic acid)) were determined by X-ray diffraction. The existence of an intramolecular hydrogen bond of enol character between the hydroxyl and acetyl groups was found by the X-ray method. The enol character was also confirmed by DFT (B3LYP/6-31+G(d,p)) calculations. A phase transition was found at 138 K in 5-chloro-3-nitro-2-hydroxyacetophenone. This phase transition was investigated by differential scanning calorimetry (DSC), dilatometry, and the dielectric method. A study of the nitro-group dynamics in the ortho-hydroxy acetophenones was carried out with DFT (B3LYP/6-31+G(d,p)) calculations.

  11. Theoretical study on molecular packing and electronic structure of bi-1,3,4-oxadiazole derivatives

    KAUST Repository

    Wang, Haitao; Bai, Fuquan; Jia, Xiaoshi; Cao, Di; Ravva, Mahesh Kumar; Bredas, Jean-Luc; Qu, Songnan; Bai, Binglian; Zhang, Hongxing; Li, Min

    2014-01-01

    The molecular aggregation structure of 5,5′-bis(naphthalen-2-yl)-2,2′-bi(1,3,4-oxadiazole) (BOXD-NP) was studied by computing the intermolecular interaction potential energy surface (PES) at density functional theory level based on a dimer model. All B3LYP, CAM-B3LYP and M062x functionals can yield a reliable isolated molecular geometry. The conformation of BOXD-NP obtained with all methods is perfectly planar, indicating good conjugation ability between oxadiazole and naphthalene rings. The vibrational frequencies of BOXD-NP were also calculated using the B3LYP/6-311+G∗∗ method, which showed great consistency with the experimental observations and makes the assignments of the IR spectra more solid. It was revealed that the lowest excited state of BOXD-NP should be assigned as a highly allowed π-π∗ state by TD-DFT calculation. Considering the non-covalent interactions in molecular aggregates, the M062x functional was applied in the construction of the PES. Besides the packing structure found in the crystals, PES also predicted several stable structures, indicating that PES has great ability in guiding molecular self-assembly. Symmetry Adapted Perturbation Theory (SAPT) analysis on these energy-minimum molecular stacking structures revealed that London dispersion forces are the strongest attractive component in the binding. This journal is

  12. Vanillin and isovanillin: Comparative vibrational spectroscopic studies, conformational stability and NLO properties by density functional theory calculations

    Science.gov (United States)

    Balachandran, V.; Parimala, K.

    This study is a comparative analysis of FT-IR and FT-Raman spectra of vanillin (3-methoxy-4-hydroxybenzaldehyde) and isovanillin (3-hydroxy-4-methoxybenzaldehyde). The molecular structure, vibrational wavenumbers, infrared intensities, Raman scattering activities were calculated for both molecules using the B3LYP density functional theory (DFT) with the standard 6-311++G∗∗ basis set. The computed values of frequencies are scaled using multiple scaling factors to yield good coherence with the observed values. The calculated harmonic vibrational frequencies are compared with experimental FT-IR and FT-Raman spectra. The geometrical parameters and total energies of vanillin and isovanillin were obtained for all the eight conformers (a-h) from DFT/B3LYP method with 6-311++G∗∗ basis set. The computational results identified the most stable conformer of vanillin and isovanillin as in the "a" form. Non-linear properties such as electric dipole moment (μ), polarizability (α), and hyperpolarizability (β) values of the investigated molecules have been computed using B3LYP quantum chemical calculation. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecules.

  13. Ferric Complexes of 3-Hydroxy-4-pyridinones Characterized by Density Functional Theory and Raman and UV−vis Spectroscopies

    Czech Academy of Sciences Publication Activity Database

    Šebestík, Jaroslav; Šafařík, Martin; Bouř, Petr

    2012-01-01

    Roč. 51, č. 8 (2012), s. 4473-4481 ISSN 0020-1669 R&D Projects: GA ČR GA203/07/1517; GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:AV ČR(CZ) M200550902 Institutional research plan: CEZ:AV0Z40550506 Keywords : Raman spectroscopy * UV-Vis spectroscopy * DFT * CAM-B3LYP * deferipron Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.593, year: 2012

  14. Molecular structure and vibrational spectra of Bis(melaminium) terephthalate dihydrate: A DFT computational study

    Science.gov (United States)

    Tanak, Hasan; Marchewka, Mariusz K.; Drozd, Marek

    2013-03-01

    The experimental and theoretical vibrational spectra of Bis(melaminium) terephthalate dihydrate were studied. The Fourier transform infrared (FT-IR) spectra of the Bis(melaminium) terephthalate dihydrate and its deuterated analogue were recorded in the solid phase. The molecular geometry and vibrational frequencies of Bis(melaminium) terephthalate dihydrate in the ground state have been calculated by using the density functional method (B3LYP) with 6-31++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The molecule contains the weak hydrogen bonds of Nsbnd H⋯O, Nsbnd H⋯N and Osbnd H⋯O types, and those bonds are calculated with DFT method. In addition, molecular electrostatic potential, frontier molecular orbitals and natural bond orbital analysis of the title compound were investigated by theoretical calculations. The lack of the second harmonic generation (SHG) confirms the presence of macroscopic center of inversion.

  15. TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

    Directory of Open Access Journals (Sweden)

    Pawel Michal Kozlowski

    2014-02-01

    Full Text Available Coenzyme B12 (AdoCbl is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM. Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl. Furthermore, potential energy surfaces (PESs obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer and a σ bonding-ligand charge transfer (SBLCT states.

  16. Angular dependence of coercivity in isotropically aligned Nd-Fe-B sintered magnets

    Science.gov (United States)

    Matsuura, Yutaka; Nakamura, Tetsuya; Sumitani, Kazushi; Kajiwara, Kentaro; Tamura, Ryuji; Osamura, Kozo

    2018-05-01

    In order to understand the coercivity mechanism in Nd-Fe-B sintered magnets, the angular dependence of the coercivity of an isotropically aligned Nd15Co1.0B6Febal. sintered magnet was investigated through magnetization measurements using a vibrating sample magnetometer. These results are compared with the angular dependence calculated under the assumption that the magnetization reversal of each grain follows the Kondorskii law or, in other words, the 1/cos θ law for isotropic alignment distributions. The calculated angular dependence of the coercivity agrees very well with the experiment for magnetic fields applied between angles of 0 and 60°, and it is expected that the magnetization reversal occurs in each grain individually followed the 1/cos θ law. In contrast, this agreement between calculation and experiment is not found for anisotropic Nd-Fe-B samples. This implies that the coercivity of the aligned magnets depends upon the de-pinning of the domain walls from pinning sites. When the de-pinning occurs, it is expected that the domain walls are displaced through several grains at once.

  17. Synthesis, physicochemical characterization, DFT calculation and biological activities of Fe(III) and Co(II)-omeprazole complexes. Potential application in the Helicobacter pylori eradication

    Science.gov (United States)

    Russo, Marcos G.; Vega Hissi, Esteban G.; Rizzi, Alberto C.; Brondino, Carlos D.; Salinas Ibañez, Ángel G.; Vega, Alba E.; Silva, Humberto J.; Mercader, Roberto; Narda, Griselda E.

    2014-03-01

    The reaction between the antiulcer agent omeprazole (OMZ) with Fe(III) and Co(II) ions was studied, observing a high ability to form metal complexes. The isolated microcrystalline solid complexes were characterized by elemental analysis, X-ray powder diffraction (XRPD), Scanning Electron Microscopy (SEM), magnetic measurements, thermal study, FTIR, UV-Visible, Mössbauer, electronic paramagnetic resonance (EPR), and DFT calculations. The metal-ligand ratio for both complexes was 1:2 determined by elemental and thermal analysis. FTIR spectroscopy showed that OMZ acts as a neutral bidentate ligand through the pyridinic nitrogen of the benzimidazole ring and the oxygen atom of the sulfoxide group, forming a five-membered ring chelate. Electronic, Mössbauer, and EPR spectra together with magnetic measurements indicate a distorted octahedral geometry around the metal ions, where the coordination sphere is completed by two water molecules. SEM and XRPD were used to characterize the morphology and the crystal nature of the complexes. The most favorable conformation for the Fe(III)-OMZ and Co(II)-OMZ complexes was obtained by DFT calculations by using B3LYP/6-31G(d)&LanL2DZ//B3LYP/3-21G(d)&LanL2DZ basis set. Studies of solubility along with the antibacterial activity against Helicobacter pylori for OMZ and its Co(II) and Fe(III) complexes are also reported. Free OMZ and both metal complexes showed antibacterial activity against H. pylori. Co(II)-OMZ presented a minimal inhibitory concentration ˜32 times lower than that of OMZ and ˜65 lower than Fe(III)-OMZ, revealing its promising potential use for the treatment of gastric pathologies associated with the Gram negative bacteria. The morphological changes observed in the cell membrane of the bacteria after the incubation with the metal-complexes were also analyzed by SEM microscopy. The antimicrobial activity of the complexes was proved by the viability test.

  18. Structure and bonding of transition metal-boryl compounds. Theoretical study of [(PH3)2(CO)ClOs-BR2] and [(PH3)2(CO)2ClOs-BR2] (BR2 = BH2, BF2, B(OH)2, B(OCH=CHO), Bcat).

    Science.gov (United States)

    Giju, K T; Bickelhaupt, F M; Frenking, G

    2000-10-16

    Quantum chemical DFT calculations using the B3LYP functionals have been carried out for the electronically unsaturated 16 VE five-coordinate osmium boryl-complexes [(PH3)2(CO)ClOs-BR2] and the 18 VE six-coordinate complexes [(PH3)2(CO)2ClOs-BR2] with BR2 = BH2, BF2, B(OH)2, B(OHC=CHO), and Bcat (cat = catecholate O2C6H4). The bonding situation of the Os-BR2 bond was analyzed with the help of the NBO partitioning scheme. The Os-B bond dissociation energies of the 16 VE complexes are very high, and they do not change very much for the different boryl ligands. The 18 VE complexes have only slightly lower bond energies than the 16 VE species. The Os-B bond in both classes of compounds is provided by a covalent sigma-bond which is polarized toward osmium and by strong charge attraction. Os-->B pi-donation is not important for the Os-B binding interactions, except for the Os-BH2 complexes. The stability of the boryl complexes [Os]-BR2 comes mainly from BB pi-donation. The intraligand charge distribution of the BR2 group changes little when the Os-B bond is formed, except for BH2. The CO ligand in [(PH3)2(CO)2ClOs-BR2] which is trans to BR2 has a relatively weak bond to the osmium atom.

  19. A comparative study on vibrational, conformational and electronic structure of 2-chloro-4-methyl-3-nitropyridine and 2-chloro-6-methylpyridine

    Science.gov (United States)

    Arjunan, V.; Saravanan, I.; Marchewka, Mariusz K.; Mohan, S.

    Experimental FTIR and FT-Raman spectroscopic analysis of 2-chloro-4-methyl-3-nitropyridine (2C4M3NP) and 2-chloro-6-methylpyridine (2C6MP) have been performed. A detailed quantum chemical calculations have been carried out using B3LYP and B3PW91 methods with 6-311++G** and cc-pVTZ basis sets. Conformation analysis was carried for 2C4M3NP and 2C6MP. The temperature dependence of thermodynamic properties has been analysed. The atomic charges, electronic exchange interaction and charge delocalisation of the molecule have been performed by natural bond orbital (NBO) analysis. Molecular electrostatic surface potential (MESP), total electron density distribution and frontier molecular orbitals (FMOs) are constructed at B3LYP/6-311++G** level to understand the electronic properties. The charge density distribution and site of chemical reactivity of the molecules have been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). The electronic properties, HOMO and LUMO energies were measured by time-dependent TD-DFT approach.

  20. Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

    Science.gov (United States)

    Ahmed, Houssem Eddine; Kamoun, Slaheddine

    2017-09-01

    The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

  1. Thiocyanate cadmium(II) complexes of 2,4,6-tri(2-pyridyl)-1,3,5-triazine – Synthesis, structure and luminescence properties

    International Nuclear Information System (INIS)

    Nawrot, I.; Machura, B.; Kruszynski, R.

    2014-01-01

    Two new thiocyanate cadmium(II) complexes of 2,4,6-tri(2-pyridyl)-1,3,5-triazine were synthesized and characterized. The resulted complexes [Cd(SCN)(NO 3 )(tptz)(H 2 O)] (1) and [Cd(SCN) 2 (tptz)(MeOH)] (2) were studied by IR, UV–vis spectroscopy and single crystal X-ray analysis. The luminescent properties of 1 and 2 were studied in solution and solid state and compared with the free ligand. To get detailed insight into the electronic structure and spectroscopic properties of [Cd(SCN)(NO 3 )(tptz)(H 2 O)] and [Cd(SCN) 2 (tptz)(MeOH)], the density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. - Highlights: • Two novel thiocyanate cadmium(II) compounds of 2,4,6-tri(2-pyridyl)-1,3,5-triazine were synthesized. • The compounds were identified by IR, UV–vis spectroscopy and X-ray analysis. • The fluorescence properties of the complexes were examined and compared with the free ligand. • The electronic spectra were investigated at the TD-DFT level employing B3LYP/LANL2DZ

  2. Spectroscopic studies and quantum chemical investigations of (3,4-dimethoxybenzylidene) propanedinitrile.

    Science.gov (United States)

    Gupta, Ujval; Kumar, Vinay; Singh, Vivek K; Kant, Rajni; Khajuria, Yugal

    2015-04-05

    The Fourier Transform Infrared (FTIR), Ultra-Violet Visible (UV-Vis) spectroscopy and Thermogravimetric (TG) analysis of (3,4-dimethoxybenzylidene) propanedinitrile have been carried out and investigated using quantum chemical calculations. The molecular geometry, harmonic vibrational frequencies, Mulliken charges, natural atomic charges and thermodynamic properties in the ground state have been investigated by using Hartree Fock Theory (HF) and Density Functional Theory (DFT) using B3LYP functional with 6-311G(d,p) basis set. Both HF and DFT methods yield good agreement with the experimental data. Vibrational modes are assigned with the help of Vibrational Energy Distribution Analysis (VEDA) program. UV-Visible spectrum was recorded in the spectral range of 190-800nm and the results are compared with the calculated values using TD-DFT approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results obtained from the studies of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are used to calculate molecular parameters like ionization potential, electron affinity, global hardness, electron chemical potential and global electrophilicity. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Rate coefficients of the CF3CHFCF3 + H → CF3CFCF3 + H2 reaction at different temperatures calculated by transition state theory with ab initio and DFT reaction paths.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2013-03-15

    The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.

  4. Theoretical studies of charge transfer and proton transfer complex formation between 3,5-dinitrobenzic acid and 1,2-dimethylimidazole

    Science.gov (United States)

    Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

    2018-05-01

    Natural atomic charge analysis and molecular electrostatic potential (MEP) surface analysis of hydrogen bonded charge transfer (HBCT) and proton transfer (PT) complex of 3,5-dinitrobenzoic acid (DNBA) and 1,2-dimethylimidazole (DMI) have been investigated by theoretical modelling using widely employed DFT/B3LYP/6-311G(d,p) level of theory. Along with this analysis, Hirshfeld surface study of the intermolecular interactions and associated 2D finger plot for reported PT complex between DNBA and DMI have been explored.

  5. Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

    Science.gov (United States)

    Alver, Özgur; Kaya, Mehmet Fatih

    2014-11-01

    Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.

  6. Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

    Science.gov (United States)

    Meng, Qingxi; Shen, Wei; Li, Ming

    2012-03-01

    Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

  7. Spectroscopic analysis and molecular docking of imidazole derivatives and investigation of its reactive properties by DFT and molecular dynamics simulations

    Science.gov (United States)

    Thomas, Renjith; Hossain, Mossaraf; Mary, Y. Sheena; Resmi, K. S.; Armaković, Stevan; Armaković, Sanja J.; Nanda, Ashis Kumar; Ranjan, Vivek Kumar; Vijayakumar, G.; Van Alsenoy, C.

    2018-04-01

    Solvent-free synthesis pathway for obtaining two imidazole derivatives (2-chloro-1-(4-methoxyphenyl)-4,5-dimethyl-1H-imidazole (CLMPDI) and 1-(4-bromophenyl)-2-chloro-4,5-dimethyl-1H-imidazole (BPCLDI) has been reported in this work, followed by detailed experimental and computational spectroscopic characterization and reactivity study. Spectroscopic methods encompassed IR, FT-Raman and NMR techniques, with the mutual comparison of experimentally and computationally obtained results at DFT/B3LYP level of theory. Reactivity study based on DFT calculations encompassed molecular orbitals analysis, followed by calculations of molecular electrostatic potential (MEP) and average local ionization energy (ALIE) values, Fukui functions and bond dissociation energies (BDE). Additionally, the stability of title molecules in water has been investigated via molecular dynamics (MD) simulations, while interactivity with aspulvinonedimethylallyl transferase protein has been evaluated by molecular docking procedure. CLMPDI compound showed antimicrobial activity against all four bacterial strain in both gram positive and gram negative bacteria while, BPCLDI showed only in gram positive bacteria, Staphylococcus Aureus (MTCC1144). The first order hyperpolarizability of CLMPDI and BPCLDI are 20.15 and 6.10 times that of the standard NLO material urea.

  8. Experimental and theoretical studies on the structure and spectroscopic properties of (E)-1-(2-aminophenyl)-3-(pyridine-4-yl) prop-2-en-1-one

    Science.gov (United States)

    Cruz Ortiz, Andrés Felipe; Sánchez López, Alberto; García Ríos, Alejandro; Cuenú Cabezas, Fernando; Rozo Correa, Ciro Eduardo

    2015-10-01

    (E)-1-(2-aminophenyl)-3-(pyridine-4-yl)prop-2-en-1-one (or simply 2-aminochalcone) was synthetized and characterized by elemental analysis, FT-IR, NMR, MS and XRD. Molecular geometry optimization, vibrational harmonic frequencies, 1H and 13C NMR chemical shifts were calculated by ab initio (HF and MP2) and density functional theory (DFT) methods, with B3LYP and B3PW91 functionals, using GAUSSIAN 09 program package without any constraint on the geometry. With VEDA software vibrational frequencies were assigned in terms of the potential energy distribution. A detailed interpretation of the FT-IR, NMR and XRD, experimental and calculated, is reported. The HOMO and LUMO energy gap that reflects the chemical activity of the molecule were also studied by DFT and above basis set. All theoretical results correspond to a great extent to experimental ones.

  9. Density functional theory investigation of opto-electronic properties of thieno[3,4-b]thiophene and benzodithiophene polymer and derivatives and their applications in solar cell

    Science.gov (United States)

    Khoshkholgh, Mehri Javan; Marsusi, Farah; Abolhassani, Mohammad Reza

    2015-02-01

    PTBs polymers with thieno[3,4-b]thiophene [TT] and benzodithiophene [BDT] units have particular properties, which demonstrate it as one of the best group of donor materials in organic solar cells. In the present work, density functional theory (DFT) is applied to investigate the optimized structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), band gap and dihedral angle of PTB7 at B3LYP/6-31G(d). Two different approaches are applied to carry out these investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method. The results obtained from PBC-DFT method are in fair agreement with experiments. Based on these reliable outcomes; the investigations continued to perform some derivatives of PTB7. In this study, sulfur is substituted by nitrogen, oxygen, silicon, phosphor or selenium atoms in pristine PTB7. Due to the shift of HOMO and LUMO levels, smaller band gaps are predicted to appear in some derivatives in comparison with PTB7. Maximum theoretical efficiencies, η, of the mentioned derivatives as well as local difference of dipole moments between the ground and excited states (Δμge) are computed. The results indicate that substitution of sulfur by nitrogen or oxygen in BDT unit, and silicon or phosphor in TT unit of pristine PTB7 leads to a higher η as well as Δμge.

  10. Structural and vibrational properties of oxcarbazepine, an anticonvulsant substance by using DFT and SCRF calculations

    Science.gov (United States)

    Ladetto, María F.; Márquez, María B.; Brandán, Silvia A.

    2014-10-01

    In this work, we have presented a structural and vibrational study on the properties in gas and aqueous solution phases of oxcarbazepine, a polymorphic anticonvulsant substance, combining the available IR and Raman spectra with Density Functional Theory (DFT) calculations. Two stable C1 and C2 forms for the title molecule were theoretically determined by using the hybrid B3LYP/6-31G* method. The integral equation formalism variant polarised continuum model (IEFPCM) was employed to study the solvent effects by means of the self-consistent reaction field (SCRF) method. The vibrational spectra for the two forms of oxcarbazepine were completely assigned together with two dimeric species also observed in the solid phase. The presences of the two C1 and C2 forms together with the two dimeric species are supported by the IR and Raman bands between 1424 and 125 cm-1. Here, the properties for both forms of oxcarbazepine are compared and discussed.

  11. Synthesis, spectroscopy, X-ray crystallography, DFT calculations, DNA binding and molecular docking of a propargyl arms containing Schiff base.

    Science.gov (United States)

    Balakrishnan, C; Subha, L; Neelakantan, M A; Mariappan, S S

    2015-11-05

    A propargyl arms containing Schiff base (L) was synthesized by the condensation of 1-[2-hydroxy-4-(prop-2-yn-1-yloxy)phenyl]ethanone with trans-1,2-diaminocyclohexane. The structure of L was characterized by IR, (1)H NMR, (13)C NMR and UV-Vis spectroscopy and by single crystal X-ray diffraction analysis. The UV-Visible spectral behavior of L in different solvents exhibits positive solvatochromism. Density functional calculation of the L in gas phase was performed by using DFT (B3LYP) method with 6-31G basis set. The computed vibrational frequencies and NMR signals of L were compared with the experimental data. Tautomeric stability study inferred that the enolimine is more stable than the ketoamine form. The charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Electronic absorption and emission spectral studies were used to study the binding of L with CT-DNA. The molecular docking was done to identify the interaction of L with A-DNA and B-DNA. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: a combined experimental and theoretical study.

    Science.gov (United States)

    Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet

    2015-01-25

    In this study, the structural and vibrational analysis of 3,4-pyridinedicarboxylic acid (3,4-PDCA) are presented using experimental techniques as FT-IR, FT-Raman, NMR, UV and quantum chemical calculations. FT-IR and FT-Raman spectra of 3,4-pyridinedicarboxylic acid in the solid phase are recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The geometrical parameters and energies of all different and possible monomer, dimer, anion(-1) and anion(-2) conformers of 3,4-PDCA are obtained from Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) basis set. There are sixteen conformers (C1C16) for this molecule (neutral form). The most stable conformer of 3,4-PDCA is the C1 conformer. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. (1)H and (13)C NMR spectra are recorded and the chemical shifts are calculated by using DFT/B3LYP methods with 6-311++G(d,p) basis set. The UV absorption spectrum of the studied compound is recorded in the range of 200-400 nm by dissolved in ethanol. The optimized geometric parameters were compared with experimental data via the X-ray results derived from complexes of this molecule. In addition these, molecular electrostatic potential (MEP), thermodynamic and electronic properties, HOMO-LUMO energies and Mulliken atomic charges, are performed. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Matrix-isolation and solid state low temperature FT-IR study of 2,3-butanedione (diacetyl)

    OpenAIRE

    Gómez-Zavaglia, Andrea; Fausto, R.

    2003-01-01

    2,3-Butanedione (diacetyl) was studied by matrix-isolation and low temperature solid state FT-IR spectroscopy, supported by molecular orbital calculations undertaken at the DFT(B3LYP) and MP2 levels of theory with the 6-311++G(d,p) basis set. Both in the crystalline phase and in the matrices, the compound exists in the C2h symmetry trans conformation (O=C-C=O dihedral angle of 180°). This form corresponds to the single conformational state predicted by the theoretical calculations for the com...

  14. Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

    International Nuclear Information System (INIS)

    Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J.R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J.L.

    2016-01-01

    Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO 2 films grown by atomic layer deposition (ALD) after reaction with OH − ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl 4 (hafnium tetrachloride), HfI 4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  15. Estudio teórico de la reactividad de las conformaciones y configuraciones de los ácidos grasos omega-3 a través de descriptores moleculares de reactividad utilizando la Teoría del Funcional de la Densidad (DFT

    Directory of Open Access Journals (Sweden)

    Jhon Zapata.

    2009-04-01

    Full Text Available La reactividad y estabilidad estructural de los ácidos omega-3, alfa-linolénico (ALA, estearidónico (SDA, eicosapentaenoico (EPA y docosahexaenoico (DHA, fue estudiada desde el punto de vista teórico haciendo uso de una serie de cálculos mecánico-cuánticos tipo DFT, usando la funcional B3LYP junto con la base de cálculo 6-31G. A través de descriptores de la reactividad química tales como, el potencial electrostático molecular (MEP, la función de Fukui, la dureza global, la suavidad global y local, energía de los orbitales HOMO-LUMO, se estudiaron algunas propiedades moleculares de los ácidos grasos omega-3, que permitió obtener información molecular valiosa acerca de los sitios reactivos y de la estabilidad estructural de este tipo de ácidos grasos.

  16. The performance of selected semi-empirical and DFT methods in studying C60 fullerene derivatives

    Science.gov (United States)

    Sikorska, Celina; Puzyn, Tomasz

    2015-11-01

    The capability of reproducing the open circuit voltages (V oc) of 15 representative C60 fullerene derivatives was tested using the selected quantum mechanical methods (B3LYP, PM6, and PM7) together with the two one-electron basis sets. Certain theoretical treatments (e.g. PM6) were found to be satisfactory for preliminary estimates of the open circuit voltages (V oc), whereas the use of the B3LYP/6-31G(d) approach has been proven to assure highly accurate results. We also examined the structural similarity of 19 fullerene derivatives by employing principle component analysis (PCA). In order to express the structural features of the studied compounds we used molecular descriptors calculated with semi-empirical (PM6 and PM7) and density functional (B3LYP/6-31G(d)) methods separately. In performing PCA, we noticed that semi-empirical methods (i.e. PM6 and PM7) seem satisfactory for molecules, in which one can distinguish the aromatic and the aliphatic parts in the cyclopropane ring of PCBM (phenyl-C61-buteric acid methyl ester) and they significantly overestimate the energy of the highest occupied molecular orbital (E HOMO). The use of the B3LYP functional, however, is recommended for studying methanofullerenes, which closely resemble the structure of PCBM, and for their modifications.

  17. The performance of selected semi-empirical and DFT methods in studying C60 fullerene derivatives

    International Nuclear Information System (INIS)

    Sikorska, Celina; Puzyn, Tomasz

    2015-01-01

    The capability of reproducing the open circuit voltages (V oc ) of 15 representative C 60 fullerene derivatives was tested using the selected quantum mechanical methods (B3LYP, PM6, and PM7) together with the two one-electron basis sets. Certain theoretical treatments (e.g. PM6) were found to be satisfactory for preliminary estimates of the open circuit voltages (V oc ), whereas the use of the B3LYP/6-31G(d) approach has been proven to assure highly accurate results. We also examined the structural similarity of 19 fullerene derivatives by employing principle component analysis (PCA). In order to express the structural features of the studied compounds we used molecular descriptors calculated with semi-empirical (PM6 and PM7) and density functional (B3LYP/6-31G(d)) methods separately. In performing PCA, we noticed that semi-empirical methods (i.e. PM6 and PM7) seem satisfactory for molecules, in which one can distinguish the aromatic and the aliphatic parts in the cyclopropane ring of PCBM (phenyl-C 61 -buteric acid methyl ester) and they significantly overestimate the energy of the highest occupied molecular orbital (E HOMO ). The use of the B3LYP functional, however, is recommended for studying methanofullerenes, which closely resemble the structure of PCBM, and for their modifications. (paper)

  18. The performance of selected semi-empirical and DFT methods in studying C₆₀ fullerene derivatives.

    Science.gov (United States)

    Sikorska, Celina; Puzyn, Tomasz

    2015-11-13

    The capability of reproducing the open circuit voltages (V(oc)) of 15 representative C60 fullerene derivatives was tested using the selected quantum mechanical methods (B3LYP, PM6, and PM7) together with the two one-electron basis sets. Certain theoretical treatments (e.g. PM6) were found to be satisfactory for preliminary estimates of the open circuit voltages (V(oc)), whereas the use of the B3LYP/6-31G(d) approach has been proven to assure highly accurate results. We also examined the structural similarity of 19 fullerene derivatives by employing principle component analysis (PCA). In order to express the structural features of the studied compounds we used molecular descriptors calculated with semi-empirical (PM6 and PM7) and density functional (B3LYP/6-31G(d)) methods separately. In performing PCA, we noticed that semi-empirical methods (i.e. PM6 and PM7) seem satisfactory for molecules, in which one can distinguish the aromatic and the aliphatic parts in the cyclopropane ring of PCBM (phenyl-C61-buteric acid methyl ester) and they significantly overestimate the energy of the highest occupied molecular orbital (E(HOMO)). The use of the B3LYP functional, however, is recommended for studying methanofullerenes, which closely resemble the structure of PCBM, and for their modifications.

  19. Synthesis, vibrational, NMR, quantum chemical and structure-activity relation studies of 2-hydroxy-4-methoxyacetophenone.

    Science.gov (United States)

    Arjunan, V; Devi, L; Subbalakshmi, R; Rani, T; Mohan, S

    2014-09-15

    The stable geometry of 2-hydroxy-4-methoxyacetophenone is optimised by DFT/B3LYP method with 6-311++G(∗∗) and cc-pVTZ basis sets. The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry have been determined. The effects of substituents (hydroxyl, methoxy and acetyl groups) on the benzene ring vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of 2-hydroxy-4-methoxyacetophenone have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. 1H and 13C NMR isotropic chemical shifts are calculated and assignments made are compared with the experimental values. The energies of important MO's, the total electron density and electrostatic potential of the compound are determined. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. A DFT study for the structural and electronic properties of Zn m Se n nanoclusters

    Science.gov (United States)

    Yadav, Phool Singh; Pandey, Dheeraj Kumar

    2012-09-01

    An ab initio study has been performed for the stability, structural and electronic properties of 19 small zinc selenide Zn m Se n ( m + n = 2-4) nanoclusters. Out of these nanoclusters, one nanocluster is found to be unstable due to its imaginary vibrational frequency. A B3LYP-DFT/6-311G(3df) method is used in the optimization of the geometries of the nanoclusters. We have calculated the zero point energy (ZPE), which is ignored by the other workers. The binding energies (BE), HOMO-LUMO gaps and bond lengths have been obtained for all the optimized nanoclusters. For the same value of ` m' and ` n', we designate the most stable structure the one, which has maximum final binding energy (FBE) per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), dipole moments and charge on atoms have been investigated for the most stable nanoclusters. For the same value of ` m' and ` n', the nanocluster containing maximum number of Se atoms is found to be most stable.

  1. Synthesis, Density Functional Theory (DFT), Urease Inhibition and Antimicrobial Activities of 5-Aryl Thiophenes Bearing Sulphonylacetamide Moieties.

    Science.gov (United States)

    Noreen, Mnaza; Rasool, Nasir; Gull, Yasmeen; Zubair, Muhammad; Mahmood, Tariq; Ayub, Khurshid; Nasim, Faiz-Ul-Hassan; Yaqoob, Asma; Zia-Ul-Haq, Muhammad; de Feo, Vincenzo

    2015-11-05

    A variety of novel 5-aryl thiophenes 4a-g containing sulphonylacetamide (sulfacetamide) groups were synthesized in appreciable yields via Pd[0] Suzuki cross coupling reactions. The structures of these newly synthesized compounds were determined using spectral data and elemental analysis. Density functional theory (DFT) studies were performed using the B3LYP/6-31G (d, p) basis set to gain insight into their structural properties. Frontier molecular orbital (FMOs) analysis of all compounds 4a-g was computed at the same level of theory to get an idea about their kinetic stability. The molecular electrostatic potential (MEP) mapping over the entire stabilized geometries of the molecules indicated the reactive sites. First hyperpolarizability analysis (nonlinear optical response) were simulated at the B3LYP/6-31G (d, p) level of theory as well. The compounds were further evaluated for their promising antibacterial and anti-urease activities. In this case, the antibacterial activities were estimated by the agar well diffusion method, whereas the anti-urease activities of these compounds were determined using the indophenol method by quantifying the evolved ammonia produced. The results revealed that all the sulfacetamide derivatives displayed antibacterial activity against Bacillus subtiles, Escherichia coli, Staphylococcus aureus, Shigella dysenteriae, Salmonella typhae, Pseudomonas aeruginosa at various concentrations. Furthermore, the compound 4g N-((5-(4-chlorophenyl)thiophen-2-yl)sulfonyl) acetamide showed excellent urease inhibition with percentage inhibition activity ~46.23 ± 0.11 at 15 µg/mL with IC50 17.1 µg/mL. Moreover, some other compounds 4a-f also exhibited very good inhibition against urease enzyme.

  2. In Silico Screening, Alanine Mutation, and DFT Approaches for Identification of NS2B/NS3 Protease Inhibitors

    Directory of Open Access Journals (Sweden)

    R. Balajee

    2016-01-01

    Full Text Available To identify the ligand that binds to a target protein with high affinity is a nontrivial task in computer-assisted approaches. Antiviral drugs have been identified for NS2B/NS3 protease enzyme on the mechanism to cleave the viral protein using the computational tools. The consequence of the molecular docking, free energy calculations, and simulation protocols explores the better ligand. It provides in-depth structural insights with the catalytic triad of His51, Asp75, Ser135, and Gly133. The MD simulation was employed here to predict the stability of the complex. The alanine mutation has been performed and its stability was monitored by using the molecular dynamics simulation. The minimal RMSD value suggests that the derived complexes are close to equilibrium. The DFT outcome reveals that the HOMO-LUMO gap of Ligand19 is 2.86 kcal/mol. Among the considered ligands, Ligand19 shows the lowest gap and it is suggested that the HOMO of Ligand19 may transfer the electrons to the LUMO in the active regions. The calculated binding energy of Ligand19 using the DFT method is in good agreement with the docking studies. The pharmacological activity of ligand was performed and satisfies Lipinski rule of 5. Moreover, the computational results are compared with the available IC50 values of experimental results.

  3. 3D geometrically isotropic metamaterial for telecom wavelengths

    DEFF Research Database (Denmark)

    Malureanu, Radu; Andryieuski, Andrei; Lavrinenko, Andrei

    2009-01-01

    of the unit cell is not infinitely small, certain geometrical constraints have to be fulfilled to obtain an isotropic response of the material [3]. These conditions and the metal behaviour close to the plasma frequency increase the design complexity. Our unit cell is composed of two main parts. The first part...... is obtained in a certain bandwidth. The proposed unit cell has the cubic point group of symmetry and being repeatedly placed in space can effectively reveal isotropic optical properties. We use the CST commercial software to characterise the “cube-in-cage” structure. Reflection and transmission spectra...

  4. Cu(II)

    African Journals Online (AJOL)

    ______. *Corresponding author. E-mail: ... package hybrid DFT/B3LYP hybrid functional level of theory with LANL2DZ basic set for copper and zinc atoms ..... Geometrical optimization ..... Dash, U.N. Analytical Chemistry: Theory and Practice.

  5. Fourier transform infrared and FT-Raman spectra, assignment, ab initio, DFT and normal co-ordinate analysis of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline.

    Science.gov (United States)

    Arjunan, V; Mohan, S

    2009-03-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline have been measured in the range 4000-400 and 4000-100cm(-1), respectively. Utilising the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compounds were carried out. The vibrational frequency which were determined experimentally are compared with those obtained theoretically from ab initio HF and DFT gradient calculations employing the HF/6-31G(d,p) and B3LYP/6-31G(d,p) methods for optimised geometries. The geometries and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The normal co-ordinate analysis was also carried out on the basis of ab initio force fields utilising Wilson's FG matrix method. The manifestations of NH-pi interactions and the influence of bulky chlorine and methyl group on the vibrational modes of the amino group are investigated.

  6. Structural characteristics and harmonic vibrational analysis of the stable conformer of 2,3-epoxypropanol by quantum chemical methods.

    Science.gov (United States)

    Arjunan, V; Rani, T; Santhanam, R; Mohan, S

    2012-10-01

    The FT-IR and FT-Raman spectra of H bond inner conformer of 2,3-epoxypropanol have been recorded in the regions 3700-400 and 3700-100 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the conformers H bond inner and H bond outer1 were optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP and MP2 methods with 6-31G** and 6-311++G** basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene) thiosemicarbazide

    Science.gov (United States)

    Zacharias, Adway Ouseph; Varghese, Anitha; Akshaya, K. B.; Savitha, M. S.; George, Louis

    2018-04-01

    A novel triazole derivative 1-(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene) thiosemicarbazide was synthesized and subjected to density functional theory (DFT) studies employing B3LYP/6-31+G(d,p) basis set. Characterization was done by FT-IR, Raman, mass, 1H NMR and 13C NMR spectroscopic analyses. The stability of the molecule was evaluated from NBO studies. Delocalization of electron charge density and hyper-conjugative interactions were accountable for the stability of the molecule. The dipole moment (μ), mean polarizabilty (△α) and first order hyperpolarizability (β) of the molecule were calculated. Molecular electrostatic potential studies, HOMO-LUMO and thermodynamic properties were also determined. HOMO and LUMO energies were experimentally determined by Cyclic Voltammetry.

  8. Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

    Science.gov (United States)

    Kaczor, Agnieszka; Almeida, Rui; Gómez-Zavaglia, Andrea; Cristiano, Maria de Lurdes S.; Fausto, Rui

    2008-03-01

    The computational description of saccharin (1,2-benzisothiazol-3(2 H)-one-1,1-dioxide) and its derivatives is difficult due to the presence of hypervalent S dbnd O bonds in their structures. Therefore, in this investigation, the HF, DFT/B3LYP and MP2 methods were used to predict the geometry and the infrared spectrum of the saccharyl derivative 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID). Their relative predictive capabilities were then evaluated by comparing the obtained results with experimentally available data, namely the newly obtained IR spectra of MBID isolated in low-temperature inert matrices. For each method, different basis sets [6-31++G(d,p), 6-31++G(3df,3pd), 6-311++G(d,p), 6-311++G(2df,2pd), 6-311++G(3df,3pd), aug-cc-pVDZ and aug-cc-pVTZ] were considered. The best overall agreement has been achieved at the B3LYP/6-311++G(3df,3pd) and B3LYP/6-31++G(3df,3pd) levels of theory, showing the adequacy of the B3LYP functional to describe the investigated properties in this type of compounds and stressing the relevance of including high-order polarization functions in the basis set. The chosen level of theory [B3LYP/6-311++G(3df,3pd)] was applied to analyze the vibrational spectra and the geometry of the title molecule. In agreement with the experiment, the C sbnd O sbnd C linkage in MBID is predicted by these calculations to exhibit considerably short (1.320 Å) and long (1.442 Å) (N dbnd )C sbnd O and (H 3)C sbnd O bonds, respectively, and a hybridization of the central oxygen atom close to sp 2 (the C sbnd O sbnd C angle is predicted to be ca. 117°). This C sbnd O sbnd C bonding pattern fits the well-known high reactivity of MBID upon thermal rearrangement, which has been shown to result in easy selective [1,3']-isomerization of the compound.

  9. Comparison of three-dimensional isotropic and conventional MR arthrography with respect to the diagnosis of rotator cuff and labral lesions: Focus on isotropic fat-suppressed proton density and VIBE sequences

    International Nuclear Information System (INIS)

    Park, S.Y.; Lee, I.S.; Park, S.K.; Cheon, S.J.; Ahn, J.M.; Song, J.W.

    2014-01-01

    Aim: To compare the diagnostic accuracies of three-dimensional (3D) isotropic magnetic resonance arthrography (MRA) using fat-suppressed proton density (PD) or volume interpolated breath-hold examination (VIBE) sequences with that of conventional MRA for the diagnosis of rotator cuff and labral lesions. Materials and methods: Eighty-six patients who underwent arthroscopic surgery were included. 3D isotropic sequences were performed in the axial plane using fat-suppressed PD (group A) in 53 patients and using VIBE (group B) in 33 patients. Reformatted images were obtained corresponding to conventional images, and evaluated for the presence of labral and rotator cuff lesions using conventional and 3D isotropic sequences. The diagnostic performances of each sequence were determined using arthroscopic findings as the standard. Results: Good to excellent interobserver agreements were obtained for both 3D isotropic sequences for the evaluation of rotator cuff and labral lesions. Excellent agreement was found between two-dimensional (2D) and 3D isotropic MRA, except for supraspinatus tendon (SST) tears by both readers and for subscapularis tendon (SCT) tears by reader 2 in group B. 2D MRA and 3D isotropic sequences had high diagnostic performances for rotator and labral tears, and the difference between the two imaging methods was insignificant. Conclusions: The diagnostic performances of 3D isotropic VIBE and PD sequences were similar to those of 2D MRA

  10. Benchmark studies of UV-vis spectra simulation for cinnamates with UV filter profile.

    Science.gov (United States)

    Garcia, Ricardo D'A; Maltarollo, Vinícius G; Honório, Káthia M; Trossini, Gustavo H G

    2015-06-01

    Skin cancer is a serious public health problem worldwide, being incident over all five continents and affecting an increasing number of people. As sunscreens are considered an important preventive measure, studies to develop better and safer sunscreens are crucial. Cinnamates are UVB filters with good efficiency and cost-benefit, therefore, their study could lead to the development of new UV filters. A benchmark to define the most suitable density functional theory (DFT) functional to predict UV-vis spectra for ethylhexyl methoxycinnamate was performed. Time-dependent DFT (TD-DFT) calculations were then carried out [B3LYP/6-311 + G(d,p) and B3P86/6-311 + G(d,p) in methanol environment] for seven cinammete derivatives implemented in the Gaussian 03 package. All DFT/TD-DFT simulations were performed after a conformational search with the Monte-Carlo method and MMFF94 force field. B3LYP and B3P86 functionals were better at reproducing closely the experimental spectra of ethylhexyl methoxycinnamate. Calculations of seven cinnamates showed a λmax of around 310 nm, corroborating literature reports. It was observed that the energy for the main electronic transition was around 3.95 eV and could be explained by electron delocalization on the aromatic ring and ester group, which is important to UV absorption. The methodology employed proved to be suitable for determination of the UV spectra of cinnamates and could be used as a tool for the development of novel UV filters.

  11. Calibration sets and the accuracy of vibrational scaling factors: A case study with the X3LYP hybrid functional

    Science.gov (United States)

    Teixeira, Filipe; Melo, André; Cordeiro, M. Natália D. S.

    2010-09-01

    A linear least-squares methodology was used to determine the vibrational scaling factors for the X3LYP density functional. Uncertainties for these scaling factors were calculated according to the method devised by Irikura et al. [J. Phys. Chem. A 109, 8430 (2005)]. The calibration set was systematically partitioned according to several of its descriptors and the scaling factors for X3LYP were recalculated for each subset. The results show that the scaling factors are only significant up to the second digit, irrespective of the calibration set used. Furthermore, multivariate statistical analysis allowed us to conclude that the scaling factors and the associated uncertainties are independent of the size of the calibration set and strongly suggest the practical impossibility of obtaining vibrational scaling factors with more than two significant digits.

  12. DFT computational analysis of piracetam

    Science.gov (United States)

    Rajesh, P.; Gunasekaran, S.; Seshadri, S.; Gnanasambandan, T.

    2014-11-01

    Density functional theory calculation with B3LYP using 6-31G(d,p) and 6-31++G(d,p) basis set have been used to determine ground state molecular geometries. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of piracetam is calculated using B3LYP/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO/NLMO analysis. The calculation of first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. Molecular electrostatic potential (MEP) at a point in the space around a molecule gives an indication of the net electrostatic effect produced at that point by the total charge distribution of the molecule. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charge is also calculated. Because of vibrational analysis, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-Vis spectra and electronic absorption properties are explained and illustrated from the frontier molecular orbitals.

  13. A study of isotropic-nematic transition of quadrupolar Gay-Berne fluid using density-functional theory approach

    Science.gov (United States)

    Singh, Ram Chandra; Ram, Jokhan

    2011-11-01

    The effects of quadrupole moments on the isotropic-nematic (IN) phase transitions are studied using the density-functional theory (DFT) for a Gay-Berne (GB) fluid for a range of length-to-breadth parameters ? in the reduced temperature range ? . The pair-correlation functions of the isotropic phase, which enter into the DFT as input parameters are found by solving the Percus-Yevick integral equation theory. The method used involves an expansion of angle-dependent functions appearing in the integral equations in terms of spherical harmonics and the harmonic coefficients are obtained by an iterative algorithm. All the terms of harmonic coefficients which involve l indices up to less than or equal to 6 are considered. The numerical accuracy of the results depends on the number of spherical harmonic coefficients considered for each orientation-dependent function. As the length-to-breadth ratio of quadrupolar GB molecules is increased, the IN transition is seen to move to lower density (and pressure) at a given temperature. It has been observed that the DFT is good to study the IN transitions in such fluids. The theoretical results have also been compared with the computer simulation results wherever they are available.

  14. Interaction between alkaline earth cations and oxo-ligands. DFT study of the affinity of the Ca2+ cation for carbonyl ligands.

    Science.gov (United States)

    da Costa, Leonardo Moreira; Carneiro, José Walkimar de Mesquita; Romeiro, Gilberto Alves; Paes, Lilian Weitzel Coelho

    2011-02-01

    The affinity of the Ca(2+) ion for a set of substituted carbonyl ligands was analyzed with both the DFT (B3LYP/6-31+G(d)) and semi-empirical (PM6) methods. Two types of ligands were studied: a set of monosubstituted [O=CH(R)] and a set of disubstituted ligands [O=C(R)(2)] (R=H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either directly bound to the carbonyl carbon atom or to the para position of a phenyl ring. The interaction energy was calculated to quantify the affinity of the Ca(2+) cation for the ligands. Geometric and electronic parameters were correlated with the intensity of the metal-ligand interaction. The electronic nature of the substituent is the main parameter that determines the interaction energy. Donor groups make the interaction energy more negative (stabilizing the complex formed), while acceptor groups make the interaction energy less negative (destabilizing the complex formed).

  15. Synthesis, DFT band structure calculations, optical and photoelectrical characterizations of the novel 5-hydroxy-4-methoxy-7-oxo-7H-furo[3,2-g]chromene-6-carbonitrile (HMOFCC)

    Science.gov (United States)

    Ibrahim, Magdy A.; Halim, Shimaa Abdel; Roushdy, N.; Farag, A. A. M.; El-Gohary, Nasser M.

    2017-11-01

    Reaction of 4-methoxy-5-oxo-5H-furo[3,2-g]chromene-6-carboxaldehyde (1) with hydroxylamine hydrochloride resulted in ring transformation producing the novel 5-hydroxy-4-methoxy-7-oxo-7H-furo[3,2-g]chromene-6-carbonitrile (HMOFCC). The structure was deduced based on its correct elemental analysis and spectral data (IR, 1H NMR, 13C NMR and mass spectra). The geometries of the HMOFCC were completely optimized by means of DFT-B3LYP/6-311++G (d,p) theoretical level. The ground state properties such as; total energy, the energy of HOMO and LUMO and Mulliken atomic charges were also determined. In addition, the two solvents; polar (methanol) and nonpolar (dioxane) were utilized to extract the electronic absorption spectra. The assignment of the detected bands was discussed by TD-DFT calculations. A cauliflower-like, as well as, needle-like leaves morphologies were observed using scanning electron microscope images. Two direct optical band gaps were extracted from the photon energy dependence of absorption coefficient at the band edges and found to be 1.16 and 2.56 eV. A characteristic emission peak of photoluminescence spectrum was observed and shifted depending on the solvent type. A remarkable rectification characteristic of HMOFCC/p-Si heterojunction confirms the diode-like behavior. The main important parameters like series resistance, shunt resistance and reverse saturation current show illumination dependence under influence of the illumination intensity range 20-100 mW/cm2. The heterojunction based HMOFCC showed phototransient properties under various illumination intensities which give the recommendation for the studied heterojunction in the field of optoelectronic device application.

  16. Design of methyldopa structure and calculation of its properties by quantum mechanics

    Directory of Open Access Journals (Sweden)

    Maziar Noei

    2017-05-01

    Full Text Available Methyldopa, which released in 1960, is one of the most popular blood pressure lowering drugs. Taking this medicine for high blood pressure, it seems that the effect drug in blood pressure duct ions convection to alpha-methyl is nor epinephrine. Alpha-methyl nor epinephrine from thus reducing central blood pressure is. This work reports an investigation of an antihypertensive drug methyldopa with the combined density functional theory (DFT and its structure was optimized at B3LYP, BLYP and MP2(3–21G∗,6–31G,6–31G∗ levels and the molecular structure in different solvents (SCRF calculation, NMR parameters were calculated using DFT at B3LYP, BLYP and MP2(3–21G∗,6–31G,6–31G∗ basis set. And finally we calculated natural bond orbital (NBO parameters for this structure.

  17. Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

    Science.gov (United States)

    Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

    2015-01-01

    The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

  18. Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Daeheum; Ko, Kyoung Chul; Lee, Jin Yong, E-mail: jinylee@skku.edu [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi [Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Nakai, Hiromi, E-mail: nakai@waseda.jp [Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); CREST, Japan Science and Technology Agency, Tokyo 102-0075 (Japan); Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520 (Japan)

    2015-01-14

    The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH and HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

  19. Galen's Anxious Patients: Lypē as Anxiety Disorder.

    Science.gov (United States)

    Mattern, Susan P

    2016-01-01

    Galen describes a syndrome he associates with an emotion called lypē, with specific symptoms and a course that may lead to humoral imbalance, disease, and death. Lypē is an emotion that encompasses distress at a loss, as the death of a close friend or the destruction of one's books by fire; but Galen also associates it with chronic worry about a future threat, and a physiology between the emotions of worry and fear (that is, 'anxiety'). Lypē can cause a progressive syndrome characterised by insomnia, fever, pallor, and weight loss that can kill patients or degenerate into psychotic illness. This syndrome can be described in modern terms as an anxiety disorder.

  20. Experimental and Computational Approaches to the Molecular Structure of 3-(2-Mercaptopyridine)phthalonitrile

    International Nuclear Information System (INIS)

    Tanak, Hasan; Koysal, Yavuz; Isik, Samil; Yaman, Hanifi; Ahsen, Vefa

    2011-01-01

    The compound 3-(2-Mercaptopyridine)phthalonitrile has been synthesized and characterized by IR, UV-vis, and X-ray single-crystal determination. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound in solvent media was examined using the B3LYP method with the 6-31G(d) basis set by applying the Onsager and polarizable continuum model. Using the TD-DFT and TD-HF methods, electronic absorption spectra of the title compound have been predicted and good agreement with the TD-DFT method and the experimental determination was found. The predicted nonlinear optical properties of the title compound are much greater than those of urea. Besides, molecular electrostatic potential of the title compound were investigated by theoretical calculations. The thermodynamic properties of the compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained

  1. Experimental and Computational Approaches to the Molecular Structure of 3-(2-Mercaptopyridine)phthalonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Tanak, Hasan [Amasya University, Amasys (Turkmenistan); Koysal, Yavuz; Isik, Samil [Ondokuz Mayis University, Samsun (Turkmenistan); Yaman, Hanifi; Ahsen, Vefa [Gebze Institute of Technology Department of Chemistry, Gebze-Kocaeli (Turkmenistan)

    2011-02-15

    The compound 3-(2-Mercaptopyridine)phthalonitrile has been synthesized and characterized by IR, UV-vis, and X-ray single-crystal determination. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound in solvent media was examined using the B3LYP method with the 6-31G(d) basis set by applying the Onsager and polarizable continuum model. Using the TD-DFT and TD-HF methods, electronic absorption spectra of the title compound have been predicted and good agreement with the TD-DFT method and the experimental determination was found. The predicted nonlinear optical properties of the title compound are much greater than those of urea. Besides, molecular electrostatic potential of the title compound were investigated by theoretical calculations. The thermodynamic properties of the compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained.

  2. DFT/TDDFT study on the electronic structure and spectral properties in annulated analogue of phenyl heteroazulene derivative

    International Nuclear Information System (INIS)

    Gasiorski, P.; Danel, K.S.; Matusiewicz, M.; Uchacz, T.; Kuźnik, W.; Piatek, Ł.; Kityk, A.V.

    2012-01-01

    Highlights: ► Cyclic voltammetry study of heteroazulene derivative PTNA. ► DFT/TDDFT/PCM calculations of molecular geometry and electronic states in PTNA. ► TDDFT/PCM calculations of the absorption and fluorescence spectra in PTNA. ► Comparison between TDDFT/PCM calculated and measured optical spectra. - Abstract: Paper reports the DFT/TDDFT study on the electronic structure and spectral properties of the seven-membered annulated heteroazulene derivative 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene (PTNA) by means of polarizable continuum model (PCM) and Lippert–Mataga–Onsager reaction field (LM-ORF) model at the B3LYP/6-31+G(d,p) level of theory. The results of calculations are compared with the measured optical absorption and fluorescence spectra as well as with the cyclic voltammetry data. The DFT/TDDFT methods exhibit rather good quantitative agreement regarding the spectral position of the first absorption band; the discrepancy between the experiment and theory is less than 0.1 eV. As for the fluorescence emission the TDDFT calculations underestimate the transition energy of about 0.45 eV. The discrepancy should be attributed to insufficient accuracy of the TDDFT optimization in the excited state. In the polar solvent environment, all the TDDFT/PCM approaches give the bathochromic (red) shift for the fluorescence emission and the hypsochromic (blue) shift for the optical absorption in accordance with the experimental observation. As for the fluorescence emission fairly good agreement with the experiment provides the hybrid approach being the combination of the TDDFT/PCM optimization with the semiempirical electronic structure calculations by PM3 method and solvation LM-ORF model predicting the emission energy in different solvents with the accuracy better than 0.06 eV.

  3. Crystal and molecular structure studies of (Z)-N-methyl-C-4-substituted phenyl nitrones by XRD, DFT, FTIR and NMR methods

    Science.gov (United States)

    Lasri, Jamal; Eltayeb, Naser Eltaher; Haukka, Matti; Alghamdi, Yousef

    2017-01-01

    (Z)-N-methyl-C-4-substituted phenyl nitrones -O+N(Me)=C(H)R (Z-2a R = 4-ClC6H4, Z-2b R = 4-NO2C6H4, Z-2c R = 4-CH3OC6H4) were synthesized and characterized by elemental analyses, FTIR, 1H, 13C and DEPT-135 NMR spectroscopy and also by single crystal X-ray diffraction (in the case of Z-2a and Z-2b). The geometries of the nitrone molecules Z-2a, Z-2b and Z-2c and their E-isomers; (E)-N-methyl-C-4-chlorophenyl nitrone E-2a, (E)-N-methyl-C-4-nitrophenyl nitrone E-2b and (E)-N-methyl-C-4-methoxyphenyl nitrone E-2c were optimized using density functional theory (DFT) at the B3LYP/6-311++G(d,p) level of theory. The theoretical vibrational frequencies obtained by DFT calculations are in good agreement with the experimental values. The electronics structures were described in terms of the distribution of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Gauge independent atomic orbital (GIAO) method was used to calculate the NMR spectra, the correlation between the calculated and experimental chemical shifts is mostly in the range of 0.94-0.97 for 1H, whereas, the correlation for 13C is 0.99. Thermodynamics study showed that the Z-isomer is favoured than E-isomer with energy barrier of 7.1, 7.2 and 7.1 kcal/mol for Z-2a, Z-2b and Z-2c, respectively. The abundance of the most stable species Z-isomers is equal to 99.99% for all three compounds at 298 K in gas phase.

  4. A Comparison of the Behavior of Functional/Basis Set Combinations for Hydrogen-Bonding in the Water Dimer with Emphasis on Basis Set Superposition Error

    OpenAIRE

    Plumley, Joshua A.; Dannenberg, J. J.

    2011-01-01

    We evaluate the performance of nine functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-DFT molecular orbital calculations and to experimenta...

  5. Synthesis, crystal structure, vibrational spectroscopy, optical properties and theoretical studies of a new organic-inorganic hybrid material: [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2.

    Science.gov (United States)

    Ben Ahmed, A; Feki, H; Abid, Y

    2014-12-10

    A new organic-inorganic hybrid material, [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2, has been synthesized and characterized by X-ray diffraction, FT-IR, Raman spectroscopy and UV-Visible absorption. The studied compound crystallizes in the triclinic system, space group P1¯ with the following parameters: a=8.4749(6)(Å), b=17.1392(12)(Å), c=17.1392(12)(Å), α=117.339(0)°, β=99.487(0)°, γ=99.487(0)° and Z=2. The crystal lattice is composed of a two discrete (BiBr6)(3-) anions surrounded by six ((CH3)2NH2)(+) cations. Complex hydrogen bonding interactions between (BiBr6)(3-) and organic cations from a three-dimensional network. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra and optical properties of the investigated molecule in the ground state. The full geometry optimization of designed system is performed using DFT method at B3LYP/LanL2DZ level of theory using the Gaussian03. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from FT-IR and Raman spectra are assigned based on the results of the theoretical calculations. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The simulated spectra satisfactorily coincide with the experimental UV-Visible spectrum. The results show good consistent with the experiment and confirm the contribution of metal orbital to the HOMO-LUMO boundary. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Fulltext PDF

    Indian Academy of Sciences (India)

    dinitroamino pyrrole derivatives were studied at the B3LYP/6-311G** level of density functional theory (DFT). The isodesmic reactions were employed to calculate the heats of formation (HOFs) for these compounds. The detonation velocity (D) and.

  7. Quantum chemical studies on structural, vibrational, nonlinear optical properties and chemical reactivity of indigo carmine dye

    Science.gov (United States)

    El-Mansy, M. A. M.

    2017-08-01

    Structural and vibrational spectroscopic studies were performed on indigo carmine (IC) isomers using FT-IR spectral analysis along with DFT/B3LYP method utilizing Gaussian 09 software. GaussView 5 program has been employed to perform a detailed interpretation of vibrational spectra. Simulation of infrared spectra has led to an excellent overall agreement with the observed spectral patterns. Mulliken population analyses on atomic charges, MEP, HOMO-LUMO, NLO, first order hyperpolarizability and thermodynamic properties have been examined by (DFT/B3LYP) method with the SDD basis set level. Density of state spectra (DOS) were calculated using GaussSum 3 at the same level of theory. Molecular modeling approved that DOS Spectra are the most significant tools for differentiating between two IC isomers so far. Moreover, The IC isomers (cis-isomer) have shown an extended applicability for manufacturing both NLO and photovoltaic devices such as solar cells.

  8. Synthesis and XRD, FT-IR vibrational, UV-vis, and nonlinear optical exploration of novel tetra substituted imidazole derivatives: A synergistic experimental-computational analysis

    Science.gov (United States)

    Ahmad, Muhammad Saeed; Khalid, Muhammad; Shaheen, Muhammad Ashraf; Tahir, Muhammad Nawaz; Khan, Muhammad Usman; Braga, Ataualpa Albert Carmo; Shad, Hazoor Ahmad

    2018-04-01

    Heterocyclic compounds have potential applications in many fields of life. We synthesized novel tetra substituted imidazoles by four-component condensation of benzil, substituted aldehydes, substituted anilines and ammonium acetate as a source of ammonia and acetic acid as the solvent. Their chemical structures were resolved through X-ray crystallographic and spectroscopic (Fourier transform IR and UV-vis) techniques. In addition to experimental analysis, density functional theory (DFT) calculations at the B3LYP/6-311 + G(d,p) level were performed on 4-bromo-2-(1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole-2-yl)phenol (1), 4-bromo-2-(1-(1-naphthalen-yl)-4,5-diphenyl-1H-imidazole-2-yl)phenol (2), and 2-(1-(2-chlorophenyl)-4,5-diphenyl-1-H-imidazole-2-yl)-6-methoxyphenol (3) to obtain the optimized geometry and spectroscopic (Fourier transform IR and UV-vis) and non-linear optical properties. Frontier molecular orbital analysis was performed at the Hartee-Fock/6-311+g(d,p) and DFT/B3LYP/6-311+G(d,p) levels of theory. Natural bond orbital (NBO) and UV-vis spectral analyses were performed at the M06-2X/6-31+G(d,p) and time-dependent DFT/B3LYP/6-311+G(d,p) levels, respectively. Overall, the DFT findings show good agreement with the experimental data. The hyper conjugative interaction network, which is responsible for the stability of compounds 1, 2 and 3 was explored by the NBO approach. The global reactivity parameters were explored with use of the energy of the frontier molecular orbitals. DFT calculations predict the first-order hyperpolarizabilities of compounds 1, 2 and 3 are 294.89 × 10-30, 219.45 × 10-30 and 146.77 × 10-30 esu, respectively. A two-state model was used to describe the non-linear optical properties of the compounds investigated.

  9. Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

    Science.gov (United States)

    Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

    2016-05-01

    The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the л to л* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

  10. Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

    Energy Technology Data Exchange (ETDEWEB)

    Asath, R. Mohamed; Premkumar, S.; Mathavan, T.; Benial, A. Milton Franklin, E-mail: miltonfranklin@yahoo.com [Department of Physics, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India); Rekha, T. N. [PG & Research Department of Physics, Lady Doak College, Madurai 625002, Tamilnadu (India); Jawahar, A. [Department of Chemistry, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India)

    2016-05-23

    The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the π to π* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

  11. Electronic properties of mixed molybdenum dichalcogenide MoTeSe: LCAO calculations and Compton spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ahuja, Ushma [Department of Electrical Engineering, Veermata Jijabai Technological Institute, H. R. Mahajani Marg, Matunga (East), Mumbai 400019, Maharashtra (India); Kumar, Kishor; Joshi, Ritu [Department of Physics, University College of Science, M.L. Sukhadia University, Udaipur 313001, Rajasthan (India); Bhavsar, D.N. [Department of Physics, Bhavan' s Seth R.A. College of Science, Khanpur, Ahmedabad 380001, Gujarat (India); Heda, N.L., E-mail: nlheda@yahoo.co.in [Department of Pure and Applied Physics, University of Kota, Kota 324007, Rajasthan (India)

    2016-07-01

    We have employed linear combination of atomic orbitals (LCAO) method to compute the Mulliken’s population (MP), energy bands, density of states (DOS) and Compton profiles for hexagonal MoTeSe. The density functional theory (DFT) and hybridization of Hartree-Fock with DFT (B3LYP) have been used within the LCAO approximation. Performance of theoretical models has been tested by comparing the theoretical momentum densities with the experimental Compton profile of MoTeSe measured using {sup 137}Cs Compton spectrometer. It is seen that the B3LYP prescription gives a better agreement with the experimental data than other DFT based approximations. The energy bands and DOS depict an indirect band gap character in MoTeSe. In addition, a relative nature of bonding in MoTeSe and its isovalent MoTe{sub 2} is discussed in terms of equal-valence-electron-density (EVED) profiles. On the basis of EVED profiles it is seen that MoTeSe is more covalent than MoTe{sub 2}.

  12. Vibrational spectra, molecular structure, natural bond orbital, first order hyperpolarizability, thermodynamic analysis and normal coordinate analysis of Salicylaldehyde p-methylphenylthiosemicarbazone by density functional method

    Science.gov (United States)

    Porchelvi, E. Elamurugu; Muthu, S.

    2015-01-01

    The thiosemicarbazone compound, Salicylaldehyde p-methylphenylthiosemicarbazone (abbreviated as SMPTSC) was synthesized and characterized by FTIR, FT-Raman and UV. Density functional (DFT) calculations have been carried out for the title compound by performing DFT level of theory using B3LYP/6-31++G(d,p) basis set. The molecular geometry and vibrational frequencies were calculated and compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using density functional theory (DFT/B3LYP) with 6-311++G(d,p) basis set. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. Thearomaticities of the phenyl rings were studied using the standard harmonic oscillator model of aromaticity (HOMA) index. Mulliken population analysis on atomic charges is also calculated. The molecule orbital contributions are studied by density of energy states (DOSs).

  13. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    Science.gov (United States)

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  14. Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: a DFT study.

    Science.gov (United States)

    Meng, Qingxi; Li, Ming

    2013-10-01

    Density functional theory (DFT) was used to investigate the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. All intermediates and transition states were optimized completely at the B3LYP/6-31+G(d,p) level. Calculated results indicated that the decarbonylative addition of phthalic anhydrides to alkynes was exergonic, and the total free energy released was -87.6 kJ mol(-1). In the five-coordinated complexes M4a and M4b, the insertion reaction of alkynes into the Ni-C bond occurred prior to that into the Ni-O bond. The nickel(0)/zinc-catalyzed decarbonylative addition was much more dominant than the nickel-catalyzed one in whole catalytic decarbonylative addition. The reaction channel CA→M1'→T1'→M2'→T2'→M3a'→M4a'→T3a1'→M5a1' →T4a1'→M6a'→P was the most favorable among all reaction pathways of the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. And the alkyne insertion reaction was the rate-determining step for this channel. The additive ZnCl2 had a significant effect, and it might change greatly the electron and geometry structures of those intermediates and transition states. On the whole, the solvent effect decreased the free energy barriers.

  15. Theoretical study (ab initio and DFT methods on acidic dissociation constant of xylenol orange in aqueous solution

    Directory of Open Access Journals (Sweden)

    F. Kiani

    2017-07-01

    Full Text Available Analytical measurement of materials requires exact knowledge of their acid dissociation constant (pKa values. In recent years, quantum mechanical calculations have been extensively used to study of acidities in the aqueous solutions and the results were compared with the experimental values. In this study, a theoretical study was carried out on xylenol orange (in water solution by ab initio method. We calculated the pKa values of xylenol orange in water, using high-level ab initio (PM3, DFT (HF, B3LYP/6-31+G(d and SCRF methods. The experimental determination of these values (pKa,s is a challenge because xylenol orange has a low solubility in water. We considered several ionization reactions and equilibriums in water that constitute the indispensable theoretical basis to calculate the pKa values of xylenol orange. The results show that the calculated pKa values have a comparable agreement with the experimentally determined pKa values. Therefore, this method can be used to predict such properties for indicators, drugs and other important molecules.

  16. 2,1,3-Benzothiadiazole: Study of its structure, energetics and aromaticity

    International Nuclear Information System (INIS)

    Miranda, Margarida S.; Matos, M. Agostinha R.; Morais, Victor M.F.; Liebman, Joel F.

    2012-01-01

    Highlights: ► Enthalpies of formation of 2,1,3-benzothiadiazole were determined. ► The structure of 2,1,3-benzothiadiazole was obtained from DFT calculations. ► Calculations allowed estimation of enthalpy of formation in gas phase. ► The aromaticity was evaluated by analysis of NICS values. - Abstract: The present work reports an experimental study on the energetics of 2,1,3-benzothiadiazole and a computational study on its structure, energetics and aromaticity. In the experimental part the standard (p° = 0.1 MPa) massic energy of combustion, at T = 298.15 K, was measured by rotating bomb combustion calorimetry, in oxygen, and allowed the calculation of the respective standard molar enthalpy of formation, in the crystalline phase, at T = 298.15 K. The standard molar enthalpy of sublimation, at T = 298.15 K, was measured by high-temperature Calvet microcalorimetry. From the combination of data obtained by both techniques we were able to calculate the respective standard molar enthalpy of formation, in the gas phase, at T = 298.15 K: (276.6 ± 2.5) kJ · mol −1 . This thermochemical parameter was compared with estimates obtained from high level ab initio quantum chemical calculations using the G3(MP2)//B3LYP composite method and various appropriately chosen reactions. The molecular structure of 2,1,3-benzothiadiazole was obtained from DFT calculations with the B3LYP density functional and various basis sets: 6-31G(d), 6-311(d,p), 6-311+G(3df,2p), aug-ccpVTZ and aug-ccpVQZ and its aromaticity and that of some related molecules were evaluated by analysis of nucleus independent chemical shifts (NICS) values.

  17. Quantum chemical investigation of attractive non-covalent interactions between halomethanes and rare gases.

    Science.gov (United States)

    McAllister, Linda J; Bruce, Duncan W; Karadakov, Peter B

    2012-11-01

    The interaction between rare gas atoms and trifluoromethylhalides and iodomethane is investigated using ab initio and density functional theory (DFT) methods: MP2, CCSD, B3LYP, M06, M06-L, M06-2X, M06-HF, X3LYP, PBE, B97-D, B3LYP-D3, and M06-L-D3, in combination with the aug-cc-pVTZ and aug-cc-pVTZ-PP basis sets. A weakly attractive interaction is observed for all complexes, whose strength increases as the rare gas and halogen bond donor become more polarizable, and as the group bound to the halogen bond donor becomes more electron-withdrawing. The separation between iodine and krypton in the complex CF(3)I···Kr, calculated at the MP2 and B3LYP-D3 levels of theory, agrees very well with recent experimental results (Stephens, S. L.; Walker, N. R.; Legon, A. C. J. Chem. Phys. 2011, 135, 224309). Analysis of the ability of theoretical methods to account for the dispersion interaction present in these complexes leads to the conclusion that MP2 and B3LYP-D3, which produce very similar results, are the better performing methods, followed by B97-D and the M06 suite of functionals; the popular B3LYP as well as X3LYP perform poorly and significantly underestimate the interaction strength. The orbitals responsible for the interaction are identified through Edmiston-Ruedenberg localization; it is shown that, by combining the key orbitals, it is possible to observe a molecular orbital picture of a σ-hole interaction.

  18. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland

    2008-01-01

    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...

  19. Superfluid H3e in globally isotropic random media

    Science.gov (United States)

    Ikeda, Ryusuke; Aoyama, Kazushi

    2009-02-01

    Recent theoretical and experimental studies of superfluid H3e in aerogels with a global anisotropy created, e.g., by an external stress have definitely shown that the A -like phase with an equal-spin pairing in such aerogel samples is in the Anderson-Brinkman-Morel (ABM) (or axial) pairing state. In this paper, the A -like phase of superfluid H3e in globally isotropic aerogel is studied in detail by assuming a weakly disordered system in which singular topological defects are absent. Through calculation of the free energy, a disordered ABM state is found to be the best candidate of the pairing state of the globally isotropic A -like phase. Further, it is found through a one-loop renormalization-group calculation that the coreless continuous vortices (or vortex-Skyrmions) are irrelevant to the long-distance behavior of disorder-induced textures, and that the superfluidity is maintained in spite of lack of the conventional superfluid long-range order. Therefore, the globally isotropic A -like phase at weak disorder is, like in the case with a globally stretched anisotropy, a glass phase with the ABM pairing and shows superfluidity.

  20. NMR and NQR study of Si-doped (6,0) zigzag single-walled aluminum nitride nanotube as n or P-semiconductors.

    Science.gov (United States)

    Baei, Mohammad T; Peyghan, Ali Ahmadi; Tavakoli, Khadijeh; Babaheydari, Ali Kazemi; Moghimi, Masoumeh

    2012-09-01

    Density functional theory (DFT) calculations were performed to investigate the electronic structure properties of pristine and Si-doped aluminum nitride nanotubes as n or P-semiconductors at the B3LYP/6-31G* level of theory in order to evaluate the influence of Si-doped in the (6,0) zigzag AlNNTs. We extended the DFT calculation to predict the electronic structure properties of Si-doped aluminum nitride nanotubes, which are very important for production of solid-state devices and other applications. To this aim, pristine and Si-doped AlNNT structures in two models (Si(N) and Si(Al)) were optimized, and then the electronic properties, the isotropic (CS(I)) and anisotropic (CS(A)) chemical shielding parameters for the sites of various (27)Al and (14)N atoms, NQR parameters for the sites of various of (27)Al and (14)N atoms, and quantum molecular descriptors were calculated in the optimized structures. The optimized structures, the electronic properties, NMR and NQR parameters, and quantum molecular descriptors for the Si(N) and Si(Al) models show that the Si(N) model is a more reactive material than the pristine or Si(Al) model.

  1. A combined molecular dynamics simulation and quantum mechanics study on mercaptopurine interaction with the cucurbit [6,7] urils: Analysis of electronic structure

    Science.gov (United States)

    Zaboli, Maryam; Raissi, Heidar

    2018-01-01

    In the current study, the probability of complex formation between mercaptopurine drug with cucurbit[6]urils and cucurbit[7]urils has been investigated. The calculations for geometry optimization of complexes have been carried out by means of DFT (B3LYP), DFT-D (B3LYP-D) and M06-2X methods. The Atoms In Molecules (AIM), Natural Bond Orbital (NBO), NMR, the density of states (DOSs) and frontier molecular orbital (MO) analyses have been done on the inclusion complexes. In addition, the UV-Vis spectra of the first eight states have been obtained by CAM-B3LYP/TD-DFT calculation. The obtained results of the complexation process reveal that CB[7]-DRG complexes are more favorable than that of CB[6]-DRG interactions. Furthermore, our theoretical results show that configurations III and I are the most stable configurations related to the CB[6]/DRG and CB[7]/DRG interactions, respectively. The positive ∇2ρ(r) and HC values at the bond critical points indicate that exist the weak H-bonds between CB[6] and CB[7] with H atoms of the drug molecule. The obtained negative binding energy values of CB[7]-DRG interaction in solution phase show the stability of these complexes in the aqueous medium. Also, all of the observed parameters of molecular dynamics simulation such as the number of contacts, hydrogen bonding, center-of-mass distance and van der Waals energy values confirm the encapsulation of mercaptopurine molecule inside the cucurbit[7]urils cavity at about 3.2 ns.

  2. FT-IR, FT-Raman spectra and ab initio HF and DFT calculations of 7-chloro-5-(2-chlorophenyl)-3-hydroxy-2,3-dihydro-1H-1,4-benzodiazepin-2-one.

    Science.gov (United States)

    Muthu, S; Prasath, M; Paulraj, E Isac; Balaji, R Arun

    2014-01-01

    The Fourier Transform infrared and Fourier Transform Raman spectra of 7-chloro-5 (2-chlorophenyl)-3-hydroxy-2,3-dihydro-1H-1,4-benzodiazepin-2-one (7C3D4B) were recorded in the regions 4000-400 and 4000-100 cm(-1), respectively. The appropriate theoretical spectrograms for the IR and Raman spectra of the title molecule were also constructed. The calculated results show that the predicted geometry can well reproduce the structural parameters. Predicted vibrational frequencies have been assigned and compared with experimental IR spectra and they supported each other. Stability of the molecule arising from hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond-like weak interaction has been analyzed using natural bond orbital (NBO) analysis by using B3LYP/6-31G(d,p) method. The results show that electron density (ED) in the σ* and π* antibonding orbitals and second-order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The first order hyperpolarizability (βtotal) of this molecular system and related properties (β, μ, and Δα) are calculated using HF/6-31G(d,p) and B3LYP/6-31G(d,p) methods based on the finite-field approach. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Application of MCD spectroscopy and TD-DFT to a highly non-planar porphyrinoid ring system. New insights on red-shifted porphyrinoid spectral bands.

    Science.gov (United States)

    Mack, John; Asano, Yoshiaki; Kobayashi, Nagao; Stillman, Martin J

    2005-12-21

    The first magnetic circular dichroism (MCD) spectra are reported for tetraphenyltetraacenaphthoporphyrin (TPTANP). The impact on the electronic structure of steric interactions between the fused acenaphthalene rings and the meso-tetraphenyl substituents is explored based on an analysis of the optical spectra of the Zn(II) complex (ZnTPTANP) and the free base dication species ([H4TPTANP]2+). In the case of ZnTPTANP, significant folding of the porphyrinoid ligand induces a highly unusual MCD-sign reversal providing the first direct spectroscopic evidence of ligand nonplanarity. Density functional theory (DFT) geometry optimizations for a wide range of Zn(II) porphyrinoids based on the B3LYP functional and TD-DFT calculations of the associated UV-visible absorption spectra are reported, allowing a complete assessment of the MCD data. TPTANP complexes are found to fall into a class of cyclic polyenes, termed as soft MCD chromophores by Michl (J. Pure Appl. Chem. 1980, 52, 1549.), since the signs of the Faraday A1 terms observed in the MCD spectrum are highly sensitive to slight structural changes. The origin of an unusually large red shift of the main B (or Soret) band of MTPTANP (the most red shifted ever reported for fused-ring-expanded metal porphines) and of similar red shifts observed in the spectra of other peripherally crowded porphyrinoid complexes is also explored and explained on this basis.

  4. QTAIM studies of [Li(DMSO){sub n}]{sup +} and [Al(DMSO){sub n}]{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Breza, Martin, E-mail: martin.breza@stuba.sk [Department Physical Chemistry, Slovak Technical University, Radlinskeho 9, SK-81237 Bratislava (Slovakia)

    2015-12-07

    Geometry optimization of [Li(DMSO){sub n}]{sup +} and [Al(DMSO){sub n}]{sup 3+} complexes with n = 1 - 6 in DMSO (dimethyl sulfoxide, (CH{sub 3}){sub 2}SO) solutions is performed using DFT treatment with B3LYP hybrid functional and cc-pVDZ basis sets. Solvent effects are approximated within Integral Equation Formalism Polarisable Continuum Model. Electron structure of individual model systems is investigated in terms of Quantum Theory of Atoms-in-Molecule topological analysis of electron density. Metal-DMSO bonding through oxygen atom is preferred. The most probable coordination numbers n = 4 for Li{sup +} and n = 6 for Al{sup 3+} complexes with DMSO are concluded.

  5. N,N′-Dipyridoxyl(1,8-diamino-3,6-dioxaoctane Schiff-base: Synthesis, experimental and theoretical identification

    Directory of Open Access Journals (Sweden)

    M.J. Khoshkholgh

    2013-05-01

    Full Text Available The N,N′-dipyridoxyl(1,8-diamino-3,6-dioxaoctane (=H2L Schiff-base has been synthesized and characterized by IR, 1H NMR, mass spectrometry and elemental analysis. Its optimized geometry and theoretical vibrational frequencies have been computed using density functional theory (DFT method via the B3LYP functional. Also, its 1H and 13C NMR chemical shifts have been calculated at the same computational level. In optimized geometry of the H2L, the two pyridine rings are perpendicular to each other. The phenolic hydrogens are engaged in intramolecular-hydrogen bonds with the azomethine nitrogens.

  6. A combined molecular dynamics simulation and quantum mechanics study on mercaptopurine interaction with the cucurbit [6,7] urils: Analysis of electronic structure.

    Science.gov (United States)

    Zaboli, Maryam; Raissi, Heidar

    2018-01-05

    In the current study, the probability of complex formation between mercaptopurine drug with cucurbit[6]urils and cucurbit[7]urils has been investigated. The calculations for geometry optimization of complexes have been carried out by means of DFT (B3LYP), DFT-D (B3LYP-D) and M06-2X methods. The Atoms In Molecules (AIM), Natural Bond Orbital (NBO), NMR, the density of states (DOSs) and frontier molecular orbital (MO) analyses have been done on the inclusion complexes. In addition, the UV-Vis spectra of the first eight states have been obtained by CAM-B3LYP/TD-DFT calculation. The obtained results of the complexation process reveal that CB[7]-DRG complexes are more favorable than that of CB[6]-DRG interactions. Furthermore, our theoretical results show that configurations III and I are the most stable configurations related to the CB[6]/DRG and CB[7]/DRG interactions, respectively. The positive ∇ 2 ρ (r) and HC values at the bond critical points indicate that exist the weak H-bonds between CB[6] and CB[7] with H atoms of the drug molecule. The obtained negative binding energy values of CB[7]-DRG interaction in solution phase show the stability of these complexes in the aqueous medium. Also, all of the observed parameters of molecular dynamics simulation such as the number of contacts, hydrogen bonding, center-of-mass distance and van der Waals energy values confirm the encapsulation of mercaptopurine molecule inside the cucurbit[7]urils cavity at about 3.2ns. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations

    Science.gov (United States)

    Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-04-01

    A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of Carbamazepine.

  8. Ba-DOPED ZnO MATERIALS: A DFT SIMULATION TO INVESTIGATE THE DOPING EFFECT ON FERROELECTRICITY

    Directory of Open Access Journals (Sweden)

    Luis H. da S. Lacerda

    2016-04-01

    Full Text Available ZnO is a semiconductor material largely employed in the development of several electronic and optical devices due to its unique electronic, optical, piezo-, ferroelectric and structural properties. This study evaluates the properties of Ba-doped wurtzite-ZnO using quantum mechanical simulations based on the Density Functional Theory (DFT allied to hybrid functional B3LYP. The Ba-doping caused increase in lattice parameters and slight distortions at the unit cell angle in a wurtzite structure. In addition, the doping process presented decrease in the band-gap (Eg at low percentages suggesting band-gap engineering. For low doping amounts, the wavelength characteristic was observed in the visible range; whereas, for middle and high doping amounts, the wavelength belongs to the Ultraviolet range. The Ba atoms also influence the ferroelectric property, which is improved linearly with the doping amount, except for doping at 100% or wurtzite-BaO. The ferroelectric results indicate the ZnO:Ba is an strong option to replace perovskite materials in ferroelectric and flash-type memory devices.

  9. Synthesis, crystal structure and DFT studies of a Zinc(II) complex of 1,3-diaminopropane (Dap), [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]n. The additional stabilizing role of S⋯π chalcogen bond

    Science.gov (United States)

    Alotaibi, Mshari A.; Alharthi, Abdulrahman I.; Zierkiewicz, Wiktor; Akhtar, Muhammad; Tahir, Muhammad Nawaz; Mazhar, Muhammad; Isab, Anvarhusein A.; Ahmad, Saeed

    2017-04-01

    A zinc(II) complex of 1,3-diaminopropane (Dap), [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]n (1) has been prepared and characterized by elemental analysis, IR, 1H &13C NMR spectroscopy, and its crystal structure was determined by X-ray crystallography. The crystal structure of 1 consists of two types of molecules, a discrete monomer and a polymeric one. In the monomeric unit, the zinc atom is bound to one terminal Dap molecule and to two N-bound thiocyanate ions, while in the polymeric unit, Dap acts as a bridging ligand forming a linear chain. The Zn(II) ions in both assume a slightly distorted tetrahedral geometry. The structures of two systems: the [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]3 complex as a model of 1 and [Zn(Dap)(NCS)2]4 as a simple polymeric structure were optimized with the B3LYP-D3 method. The DFT results support that the experimentally determined structure (1) is more stable in comparison to a simple polymeric structure, [Zn(Dap)(NCS)2]n (2). The interaction energies (ΔE) for NCS anions obtained by B3LYP-D3 method are about -145 kcal mol-1, while the calculated ΔE values for neutral organic ligands are about twice smaller. The X-ray structure of 1 shows that the complex is stabilized mainly by hydrogen bonds. We also found that weak chalcogen bonds play an additional role in stabilization of compound 1. Some of the intermolecular S⋯N distances are smaller than the sum of the van der Waals radii of the corresponding atoms. To the best of our knowledge, this is the first study that shows the structure where the trivalent sulfur is involved in formation of a S⋯π chalcogen bond. The NBO and NCI analyses confirm the existence of this kind of interactions.

  10. DFT Studies on Interaction between Lanthanum and Hydroxyamide

    Science.gov (United States)

    Pati, Anindita; Kundu, T. K.; Pal, Snehanshu

    2018-03-01

    Extraction and separation of individual rare earth elements has been a challenge as they are chemically very similar. Solvent extraction is the most suitable way for extraction of rare earth elements. Acidic, basic, neutral, chelating are the major classes of extractants for solvent extraction of rare earth elements. The coordination complex of chelating extractants is very selective with positively charged metal ion. Hence they are widely used. Hydroxyamide is capable of forming chelates with metal cations. In this present study interactions of hydroxyamide ligand with lanthanum have been investigated using density functional theory (DFT). Two different functional such as raB97XD and B3LYP are applied along with 6-31+G(d,p) basis set for carbon, nitrogen, hydrogen and SDD basis set for lanthanum. Stability of formed complexes has been evaluated based on calculated interaction energies and solvation energies. Frontier orbital (highest occupied molecular orbital or HOMO and lowest unoccupied molecular orbital or LUMO) energies of the molecule have also been calculated. Electronegativity, chemical hardness, chemical softness and chemical potential are also determined for these complexes to get an idea about the reactivity. From the partial charge distribution it is seen that oxygen atoms in hydroxyamide have higher negative charge. The double bonded oxygen atom present in the hydroxyamide structure has higher electron density and so it forms bond with lanthanum but the singly bonded oxygen atom in the hydroxyamide structure is weaker donor atom and so it is less available for interaction with lanthanum.

  11. Isotropic 3D cardiac cine MRI allows efficient sparse segmentation strategies based on 3D surface reconstruction.

    Science.gov (United States)

    Odille, Freddy; Bustin, Aurélien; Liu, Shufang; Chen, Bailiang; Vuissoz, Pierre-André; Felblinger, Jacques; Bonnemains, Laurent

    2018-05-01

    Segmentation of cardiac cine MRI data is routinely used for the volumetric analysis of cardiac function. Conventionally, 2D contours are drawn on short-axis (SAX) image stacks with relatively thick slices (typically 8 mm). Here, an acquisition/reconstruction strategy is used for obtaining isotropic 3D cine datasets; reformatted slices are then used to optimize the manual segmentation workflow. Isotropic 3D cine datasets were obtained from multiple 2D cine stacks (acquired during free-breathing in SAX and long-axis (LAX) orientations) using nonrigid motion correction (cine-GRICS method) and super-resolution. Several manual segmentation strategies were then compared, including conventional SAX segmentation, LAX segmentation in three views only, and combinations of SAX and LAX slices. An implicit B-spline surface reconstruction algorithm is proposed to reconstruct the left ventricular cavity surface from the sparse set of 2D contours. All tested sparse segmentation strategies were in good agreement, with Dice scores above 0.9 despite using fewer slices (3-6 sparse slices instead of 8-10 contiguous SAX slices). When compared to independent phase-contrast flow measurements, stroke volumes computed from four or six sparse slices had slightly higher precision than conventional SAX segmentation (error standard deviation of 5.4 mL against 6.1 mL) at the cost of slightly lower accuracy (bias of -1.2 mL against 0.2 mL). Functional parameters also showed a trend to improved precision, including end-diastolic volumes, end-systolic volumes, and ejection fractions). The postprocessing workflow of 3D isotropic cardiac imaging strategies can be optimized using sparse segmentation and 3D surface reconstruction. Magn Reson Med 79:2665-2675, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

  12. Preparation and characterizations of SnO2 nanopowder and spectroscopic (FT-IR, FT-Raman, UV-Visible and NMR) analysis using HF and DFT calculations.

    Science.gov (United States)

    Ayeshamariam, A; Ramalingam, S; Bououdina, M; Jayachandran, M

    2014-01-24

    In this work, pure and singe phase SnO2 Nano powder is successfully prepared by simple sol-gel combustion route. The photo luminescence and XRD measurements are made and compared the geometrical parameters with calculated values. The FT-IR and FT-Raman spectra are recorded and the fundamental frequencies are assigned. The optimized parameters and the frequencies are calculated using HF and DFT (LSDA, B3LYP and B3PW91) theory in bulk phase of SnO2 and are compared with its Nano phase. The vibrational frequency pattern in nano phase gets realigned and the frequencies are shifted up to higher region of spectra when compared with bulk phase. The NMR and UV-Visible spectra are simulated and analyzed. Transmittance studies showed that the HOMO-LUMO band gap (Kubo gap) is reduced from 3.47 eV to 3.04 eV while it is heated up to 800°C. The Photoluminescence spectra of SnO2 powder showed a peak shift towards lower energy side with the change of Kubo gap from 3.73 eV to 3.229 eV for as-prepared and heated up to 800°C. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

  13. DFT Study of PH3 Physisorption and Chemisorptions on Boron Nitride Nanotubes

    Science.gov (United States)

    Rakhshi, Mahdi; Mohsennia, Mohsen; Rasa, Hossein

    2018-03-01

    The adsorption of PH3 molecules on the NiB,N-doped(4,4) and (5,5) BNNTS surfaces has been investigated using density functional theory (DFT). The adsorption energies, geometric and electronic structures of the adsorbed systems were studied to judge the possible application of NiB,N-doped BNNTS in PH3 monitoring systems. Our calculated results showed that NiB,N-doped BNNTS had much higher adsorption energy and shorter binding distances than pure BNNTS owning to chemisorptions of the PH3 molecule. The obtained density of states (DOS) and frontier orbitals demonstrated that the orbital hybridization was obvious between the PH3 molecule and NiB,N-doped BNNTS. However, due to weak physisorption according to the total electron density maps, there was no evidence for hybridization between PH3 molecule and pure BNNTS. It was shown that after doping of Ni atom, the primary symmetry of BNNTS decreased which enhanced the chemical activity of BNNTS towards PH3 molecules. According to the obtained results, we highlight the high potential application of NiB,N-doped BNNTS in the design and fabrication of PH3 sensing devices.

  14. Spectroscopic, DFT, and XRD Studies of Hydrogen Bonds in N-Unsubstituted 2-Aminobenzamides.

    Science.gov (United States)

    Mphahlele, Malose Jack; Maluleka, Marole Maria; Rhyman, Lydia; Ramasami, Ponnadurai; Mampa, Richard Mokome

    2017-01-04

    The structures of the mono- and the dihalogenated N -unsubstituted 2-aminobenzamides were characterized by means of the spectroscopic (¹H-NMR, UV-Vis, FT-IR, and FT-Raman) and X-ray crystallographic techniques complemented with a density functional theory (DFT) method. The hindered rotation of the C(O)-NH₂ single bond resulted in non-equivalence of the amide protons and therefore two distinct resonances of different chemical shift values in the ¹H-NMR spectra of these compounds were observed. 2-Amino-5-bromobenzamide ( ABB ) as a model confirmed the presence of strong intramolecular hydrogen bonds between oxygen and the amine hydrogen. However, intramolecular hydrogen bonding between the carbonyl oxygen and the amine protons was not observed in the solution phase due to a rapid exchange of these two protons with the solvent and fast rotation of the Ar-NH₂ single bond. XRD also revealed the ability of the amide unit of these compounds to function as a hydrogen bond donor and acceptor simultaneously to form strong intermolecular hydrogen bonding between oxygen of one molecule and the NH moiety of the amine or amide group of the other molecule and between the amine nitrogen and the amide hydrogen of different molecules. DFT calculations using the B3LYP/6-311++G(d,p) basis set revealed that the conformer ( A ) with oxygen and 2-amine on the same side predominates possibly due to the formation of a six-membered intramolecular ring, which is assisted by hydrogen bonding as observed in the single crystal XRD structure.

  15. Spectroscopic, DFT, and XRD Studies of Hydrogen Bonds in N-Unsubstituted 2-Aminobenzamides

    Directory of Open Access Journals (Sweden)

    Malose Jack Mphahlele

    2017-01-01

    Full Text Available The structures of the mono- and the dihalogenated N-unsubstituted 2-aminobenzamides were characterized by means of the spectroscopic (1H-NMR, UV-Vis, FT-IR, and FT-Raman and X-ray crystallographic techniques complemented with a density functional theory (DFT method. The hindered rotation of the C(O–NH2 single bond resulted in non-equivalence of the amide protons and therefore two distinct resonances of different chemical shift values in the 1H-NMR spectra of these compounds were observed. 2-Amino-5-bromobenzamide (ABB as a model confirmed the presence of strong intramolecular hydrogen bonds between oxygen and the amine hydrogen. However, intramolecular hydrogen bonding between the carbonyl oxygen and the amine protons was not observed in the solution phase due to a rapid exchange of these two protons with the solvent and fast rotation of the Ar–NH2 single bond. XRD also revealed the ability of the amide unit of these compounds to function as a hydrogen bond donor and acceptor simultaneously to form strong intermolecular hydrogen bonding between oxygen of one molecule and the NH moiety of the amine or amide group of the other molecule and between the amine nitrogen and the amide hydrogen of different molecules. DFT calculations using the B3LYP/6-311++G(d,p basis set revealed that the conformer (A with oxygen and 2-amine on the same side predominates possibly due to the formation of a six-membered intramolecular ring, which is assisted by hydrogen bonding as observed in the single crystal XRD structure.

  16. A DFT study of the effects of Sc doping on electronic and optical properties of CdS nanoparticles

    Directory of Open Access Journals (Sweden)

    Ur Rehman Shafiq

    2015-12-01

    Full Text Available In the present work a systematic study was carried out to understand the influence of Sc doping on electronic and optical properties of CdS nanoparticles. The geometry optimization and symmetry computation for CdS and Sc doped CdS nanoparticles using Density Functional Theory (DFT on B3LYP level with the QZ4P for Cd and DZ2P for sulphur and Sc were performed by Amsterdam Density Functional (ADF. The results show that HOMO-LUMO gap as well as electronic and optical properties of CdS clusters vary with Sc doping. The HOMO-LUMO gap is affected by the dopant and its value decreases to 0.6 eV. Through considering the numerical integration scheme in the ADF package, we investigated different vibrational modes and our calculated Raman and IR spectra are consistent with the reported result. The calculated IR and Raman peaks of CdS and Sc doped CdS clusters were in the range of 100 to 289 cm−1, 60 cm−1 to 350 cm−1 and 99 cm−1 to 282 cm−1, 60 cm−1 to 350 cm−1, respectively, which was also confirmed by experiment as well as a blue shift occurrence. Subsequently, for deeper research of pure and doped CdS clusters, their absorption spectra were calculated using time-dependent DFT method.

  17. Hydrogen and dihydrogen bonding of transition metal hydrides

    Science.gov (United States)

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  18. Hydrogen and dihydrogen bonding of transition metal hydrides

    International Nuclear Information System (INIS)

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

  19. Conformational analysis, spectroscopic, structure-activity relations and quantum chemical simulation studies of 4-(trifluoromethyl)benzylamine

    Science.gov (United States)

    Arjunan, V.; Devi, L.; Mohan, S.

    2018-05-01

    The FT-IR and FT-Raman spectra of 4-trifluoromethylbenzylamine (TFMBA) have been recorded in the range 4000-450 and 4000-100 cm-1 respectively. The conformational analysis of the compound has been carried out to attain stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers obtained theoretically from the B3LYP gradient calculations employing the standard high level 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The 1H (400 MHz; CDCl3) and 13C (100 MHz; CDCl3) nuclear magnetic resonance (NMR) spectra were also recorded. The electronic properties, highest occupied molecular orbital and lowest unoccupied molecular orbital energies are measured by DFT approach. The charges of the atoms by natural bond orbital (NBO) analysis are determined by B3LYP/cc-pVTZ method. The structure-chemical reactivity relations of the compound are determined through chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods.

  20. Benchmarking semiempirical and DFT methods for the interaction of thiophene and diethyl sulfide molecules with a Ti(OH)4(H2O) cluster.

    Science.gov (United States)

    Vorontsov, Alexander V; Smirniotis, Panagiotis G

    2017-08-01

    Semiempirical methods pm6 and pm7 as well as density functional theory functionals exchange LSDA, exchange-correlation PW91 and PBE, hybrid B3LYP1 and PBE0 were compared for energy and geometry of thiophene, diethyl sulfide (DES) molecules and their binding to a frozen Ti(OH) 4 (H 2 O) complex having one coordinatively unsaturated Ti 5C site representing small fragment of TiO 2 anatase (001) surface. PBE0/6-31G(d) with DFT-D3 dispersion correction was the best method for description of thiophene and DES molecules geometries as comparison with experimental data demonstrated. Semiempirical methods pm6 and pm7 resulted in only three of four possible binding configurations of thiophene with the Ti(OH) 4 (H 2 O) complex while pm7 described correctly the enthalpy and all configurations of DES binding with the Ti(OH) 4 (H 2 O) complex. SBKJC pseudopotential and LSDA with and without dispersion correction produced flawed results for many configurations. PBE0 and PBE with and without dispersion correction and PW91 with 6-31G(d) basis set systematically produced dependable results for thiophene and DES binding to the Ti(OH) 4 (H 2 O) complex. PBE0-D3/6-31G(d), B3LYP1-D3/6-31G(d), and PBE-D3/6-31G(d) gave best match of binding energy for thiophene while PBE0/6-31G(d) gave best match of DES binding energy as comparison with CCSD(T) energy demonstrated. On the basis of the superior results obtained with PBE0/6-31G(d), it is the recommended method for modeling of adsorption over TiO 2 surfaces. Such a conclusion is in agreement with recent literature.

  1. Li interactions with the B40 fullerene and its application in Li-ion batteries: DFT studies

    Science.gov (United States)

    Moradi, Morteza; Bagheri, Zargham; Bodaghi, Ali

    2017-05-01

    The interaction of Li and Li+ with a B40 all-boron fullerene was theoretically investigated at the B3LYP, and Minnesota 2006 levels of theory. It was found that, unexpectedly, the interaction Li+ cation with the electron deficient B40 fullerene is stronger than the Li atom. It indicates that the B40 fullerene does not act as a conventional Lewis acid because of its highly correlated structure. Frontier molecular orbitals, partial density of states, and natural bond orbital analyses were used to discuss this unusual behavior. Our calculations indicate that this behavior makes the B40 fullerene more appropriate for application in the Li-ion batteries as anode material. The calculated cell voltage is about 530 mV. Also, it was found that Hartree Fock (HF) exchange percentage of density functionals has a reverse effect on the adsorption energies of Li and Li+. This energy is increased and decreased, respectively, for Li+ and Li adsorptions by increasing %HF exchange. Finally, a potential energy surface for Li and Li+ penetration into B40 fullerene was predicted.

  2. Which Density Functional Should Be Used to Describe Protonated Water Clusters?

    Science.gov (United States)

    Shi, Ruili; Huang, Xiaoming; Su, Yan; Lu, Hai-Gang; Li, Si-Dian; Tang, Lingli; Zhao, Jijun

    2017-04-27

    Protonated water cluster is one of the most important hydrogen-bond network systems. Finding an appropriate DFT method to study the properties of protonated water clusters can substantially improve the economy in computational resources without sacrificing the accuracy compared to high-level methods. Using high-level MP2 and CCSD(T) methods as well as experimental results as benchmark, we systematically examined the effect of seven exchange-correlation GGA functionals (with BLYP, B3LYP, X3LYP, PBE0, PBE1W, M05-2X, and B97-D parametrizations) in describing the geometric parameters, interaction energies, dipole moments, and vibrational properties of protonated water clusters H + (H 2 O) 2-9,12 . The overall performance of all these functionals is acceptable, and each of them has its advantage in certain aspects. X3LYP is the best to describe the interaction energies, and PBE0 and M05-2X are also recommended to investigate interaction energies. PBE0 gives the best anharmonic frequencies, followed by PBE1W, B97-D and BLYP methods. PBE1W, B3LYP, B97-D, and X3LYP can yield better geometries. The capability of B97-D to distinguish the relative energies between isomers is the best among all the seven methods, followed by M05-2X and PBE0.

  3. Synthesis, vibrational and quantum chemical investigations of hydrogen bonded complex betaine dihydrogen selenite

    Science.gov (United States)

    Arjunan, V.; Marchewka, Mariusz K.; Kalaivani, M.

    2012-10-01

    The molecular complex of betaine with selenious acid namely, betaine dihydrogen selenite (C5H13NO5Se, BDHSe) was synthesised by the reaction of betaine and SeO2 in a 1:1:1 solution of isopropanol, methanol and water. Crystals were grown from this solution by cooling to 253 K for few days. The complex was formed without accompanying proton transfer from selenious acid molecule to betaine. The complete vibrational assignments and analysis of BDHSe have been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP) method using 6-311++G∗∗, 6-31G∗∗, cc-pVDZ and 3-21G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of BDHSe were determined by the DFT method. The 1H and 13C isotropic chemical shifts (δ ppm) of BDHSe with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. SHG experiment was carried out using Kurtz-Perry powder technique. The efficiency of second harmonic generation for BDHSe was estimated relatively to KDP: deff = 0.97 deff (KDP).

  4. Qualitative and quantitative assessment of wrist MRI at 3.0T - Comparison between isotropic 3D turbo spin echo and isotropic 3D fast field echo and 2D turbo spin echo

    International Nuclear Information System (INIS)

    Jung, Jee Young; Yoon, Young Cheol; Jung, Jin Young; Choe, Bong-Keun

    2013-01-01

    Background: Isotropic three-dimensional (3D) magnetic resonance imaging (MRI) has been applied to various joints. However, comparison for image quality between isotropic 3D MRI and two-dimensional (2D) turbo spin echo (TSE) sequence of the wrist at a 3T MR system has not been investigated. Purpose: To compare the image quality of isotropic 3D MRI including TSE intermediate-weighted (VISTA) sequence and fast field echo (FFE) sequence with 2D TSE intermediate-weighted sequence of the wrist joint at 3.0 T. Material and Methods: MRI was performed in 10 wrists of 10 healthy volunteers with isotropic 3D sequences (VISTA and FFE) and 2D TSE intermediate-weighted sequences at 3.0 T. The signal-to-noise ratio (SNR) was obtained by imaging phantom and noise-only image. Contrast ratios (CRs) were calculated between fluid and cartilage, triangular fibrocartilage complex (TFCC), and the scapholunate ligament. Two radiologists independently assessed the visibility of TFCC, carpal ligaments, cartilage, tendons and nerves with a four-point grading scale. Statistical analysis to compare CRs (one way ANOVA with a Tukey test) and grades of visibility (Kruskal-Wallis test) between three sequences and those for inter-observer agreement (kappa analysis) were performed. Results: The SNR of 2D TSE (46.26) was higher than those of VISTA (23.34) and 3D FFE (19.41). CRs were superior in 2D TSE than VISTA (P = 0.02) for fluid-cartilage and in 2D TSE than 3D FFE (P < 0.01) for fluid-TFCC. The visibility was best in 2D TSE (P < 0.01) for TFCC and in VISTA (P = 0.01) for scapholunate ligament. The visibility was better in 2D TSE and 3D FFE (P 0.04) for cartilage and in VISTA than 3D FFE (P < 0.01) for TFCC. The inter-observer agreement for the visibility of anatomic structures was moderate or substantial. Conclusion: Image quality of 2D TSE was superior to isotropic 3D MR imaging for cartilage, and TFCC. 3D FFE has better visibility for cartilage than VISTA and VISTA has superior visibility for

  5. Qualitative and quantitative assessment of wrist MRI at 3.0T - Comparison between isotropic 3D turbo spin echo and isotropic 3D fast field echo and 2D turbo spin echo

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Jee Young [Dept. of Radiology, Chungang Univ. Hospital, School of Medicine, Chungang Univ. (Korea, Republic of); Yoon, Young Cheol [Dept. of Radiology, Samsung Medical Center, School of Medicine, Sungkyunkwan Univ. (Korea, Republic of)], e-mail: ycyoon@skku.edu; Jung, Jin Young [Dept. of Radiology, Saint Paul' s Hospital, The Catholic Univ. (Korea, Republic of); Choe, Bong-Keun [Dept. of Preventive Medicine, School of Medicine, Kyung Hee Univ., Seoul (Korea, Republic of)

    2013-04-15

    Background: Isotropic three-dimensional (3D) magnetic resonance imaging (MRI) has been applied to various joints. However, comparison for image quality between isotropic 3D MRI and two-dimensional (2D) turbo spin echo (TSE) sequence of the wrist at a 3T MR system has not been investigated. Purpose: To compare the image quality of isotropic 3D MRI including TSE intermediate-weighted (VISTA) sequence and fast field echo (FFE) sequence with 2D TSE intermediate-weighted sequence of the wrist joint at 3.0 T. Material and Methods: MRI was performed in 10 wrists of 10 healthy volunteers with isotropic 3D sequences (VISTA and FFE) and 2D TSE intermediate-weighted sequences at 3.0 T. The signal-to-noise ratio (SNR) was obtained by imaging phantom and noise-only image. Contrast ratios (CRs) were calculated between fluid and cartilage, triangular fibrocartilage complex (TFCC), and the scapholunate ligament. Two radiologists independently assessed the visibility of TFCC, carpal ligaments, cartilage, tendons and nerves with a four-point grading scale. Statistical analysis to compare CRs (one way ANOVA with a Tukey test) and grades of visibility (Kruskal-Wallis test) between three sequences and those for inter-observer agreement (kappa analysis) were performed. Results: The SNR of 2D TSE (46.26) was higher than those of VISTA (23.34) and 3D FFE (19.41). CRs were superior in 2D TSE than VISTA (P = 0.02) for fluid-cartilage and in 2D TSE than 3D FFE (P < 0.01) for fluid-TFCC. The visibility was best in 2D TSE (P < 0.01) for TFCC and in VISTA (P = 0.01) for scapholunate ligament. The visibility was better in 2D TSE and 3D FFE (P 0.04) for cartilage and in VISTA than 3D FFE (P < 0.01) for TFCC. The inter-observer agreement for the visibility of anatomic structures was moderate or substantial. Conclusion: Image quality of 2D TSE was superior to isotropic 3D MR imaging for cartilage, and TFCC. 3D FFE has better visibility for cartilage than VISTA and VISTA has superior visibility for

  6. Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone

    DEFF Research Database (Denmark)

    Gorski, Alexander; Posokhov, Yevgen; Hansen, Bjarke Knud Vilster

    2006-01-01

    achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining...

  7. Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation

    DEFF Research Database (Denmark)

    Fristrup, Peter; Lassen, Peter Rygaard; Tanner, David Ackland

    2008-01-01

    obtained using DFT/B3LYP calculations, and the differences between experiment and theory are discussed. The absolute configuration at the benzylic position was established as being (R), (S) and (R) for the cis, trans and geminal dimethylsubstituted phenyloxiranes, respectively. In all three cases...

  8. On the convergence of zero-point vibrational corrections to nuclear shieldings and shielding anisotropies towards the complete basis set limit in water

    DEFF Research Database (Denmark)

    Faber, Rasmus; Buczek, Aneta; Kupka, Teobald

    2017-01-01

    ), coupled cluster singles and doubles (CCSD), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)) and Kohn-Sham density functional theory (DFT) with the B3LYP exchange-correlation functional methods in combination with the second order vibrational perturbation theory (VPT2...

  9. The ground state hydrogen conformations and vibrational analysis of 2-, 3-, 4- and 5- dihydroxybenzaldehyde: A DFT study

    International Nuclear Information System (INIS)

    Cirak, C.; Saglam, A.; Ucun, F.

    2010-01-01

    The ground state hydrogen conformations of 2-, 3-, 4- and 5-dihydroxybenzaldehyde have been investigated using density functional theory (B3LYP) methods with 6-31G (d,p) basis set. The calculations have indicated that the compounds in the ground state exist with the carbonyl group O atom linked intra molecularly by the two hydrogen bonds of the two hydroxyl groups. The vibrational analyses of the ground state conformers of all the compounds were done and their optimized geometry parameters were given.

  10. Spectral and quantum chemical studies on 1,3-bis(N(1)-4-amino-6-methoxypyrimidinebenzenesulfonamide-2,2,4,4-ethane-1,2-dithiol)-2,4-dichlorocyclodiphosph(V)azane and its erbium complex.

    Science.gov (United States)

    Al-Mogren, Muneerah M; Alaghaz, Abdel-Nasser M A; El-Gogary, Tarek M

    2014-01-24

    Novel 1,3-bis(N(1)-4-amino-6-methoxypyrimidine-benzenesulfonamide-2,2,4,4-ethane-1,2-dithiol)-2,4-dichlorocyclodiphosph(V)azane (L), was prepared and their coordinating behavior towards the lanthanide ion Er(III) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV-VIS., (1)H NMR, (13)C NMR, (31)P NMR, SEM, XRD, mass spectra, effective magnetic susceptibility measurements and thermogravimetric analysis (TGA). Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of L and its binuclear Er(III) complex. Different tautomers of the ligand were optimized at the ab initio DFT level. Keto-form structure is about 17.7 kcal/mol more stable than the enol form (taking zpe correction into account). Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which compared by the measured electronic spectra. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Kinetics and thermodynamics of the reaction between the •OH radical and adenine – a theoretical investigation

    DEFF Research Database (Denmark)

    Milhøj, Birgitte Olai; Sauer, Stephan P. A.

    2015-01-01

    the computational method is validated by considering the hydrogen abstraction from the heterocyclic N9 nitrogen in adenine as a test system. Geometries for all molecules in the reaction are optimised with four different DFT exchange-correlation functionals (B3LYP, BHandHLYP, M06-2X and wB97X-D), in combination...

  12. Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols and Hydroxide Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Santilli, Carola; Makarov, Ilya; Fristrup, Peter

    2016-01-01

    reaction is most likely involved in this case. The kinetic isotope effect was determined to be 0.67 using 1-butanol as the substrate. A plausible catalytic cycle was characterized by DFT/B3LYP-D3 and involved coordination of the alcohol to the metal, β-hydride elimination, hydroxide attack...

  13. Pd (II) complexes of bidentate chalcone ligands: Synthesis, spectral, thermal, antitumor, antioxidant, antimicrobial, DFT and SAR studies

    Science.gov (United States)

    Gaber, Mohamed; Awad, Mohamed K.; Atlam, Faten M.

    2018-05-01

    The ligation behavior of two chalcone ligands namely, (E)-3-(4-chlorophenyl)-1-(pyridin-2-yl)prop-2-en-1-one (L1) and (E)-3-(4-methoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (L2), towards the Pd(II) ion is determined. The structures of the complexes are elucidated by elemental analysis, spectral methods (IR, electronic and NMR spectra) as well as the conductance measurements and thermal analysis. The metal complexes exhibit a square planar geometrical arrangement. The kinetic and thermodynamic parameters for some selected decomposition steps have been calculated. The antimicrobial, antioxidant and anticancer activities of the chalcones and their Pd(II) complexes have been evaluated. Molecular orbital computations are performed using DFT at B3LYP level with 6-31 + G(d) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations are performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry. Thermodynamic parameters for the investigated compounds are also studied. The calculations confirm that the investigated complexes have square planner geometry, which is in a good agreement with the experimental observation.

  14. Synthesis and characterization of an anticoagulant 4-hydroxy-1-thiocoumarin by FTIR, FT-Raman, NMR, DFT, NBO and HOMO-LUMO analysis

    Science.gov (United States)

    Arjunan, V.; Santhanam, R.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

    2013-04-01

    Experimental and theoretical investigations on the molecular structural, electronic and the vibrational characteristics of 4-hydroxy-1-thiocoumarin are presented. Conformational analysis was carried out to obtain the more stable configuration of the compound. The vibrational frequencies were obtained by DFT/B3LYP calculations employing 6-311++G(d,p), 6-31G(d,p), cc-pVTZ basic sets and B3PW91 method with 6-311++G(d,p) basis set and are compared with FTIR and FT-Raman spectral data recorded in the region of 4000-400 and 4000-100 cm-1, respectively. The total electron density and molecular electrostatic potential surfaces of the molecule were constructed to display electrostatic potential (electron + nuclei) distribution. The electronic properties HOMO and LUMO energies were measured. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated by using the Gauge-Independent Atomic Orbital (GIAO) method and analyzed. The picture of localized bonds and lone pairs, stabilization energy of the delocalization of electrons, the charge and hybridisation of the atoms of 4-hydroxy-1-thiocoumarin were clearly explained by NBO analysis.

  15. Order-disorder phase transitions and their influence on the structure and vibrational properties of new hybrid material: 2-Amino-4-methyl-3-nitropyridinium trifluoroacetate

    International Nuclear Information System (INIS)

    Lorenc, J.; Bryndal, I.; Syska, W.; Wandas, M.; Marchewka, M.; Pietraszko, A.; Lis, T.; Maczka, M.; Hermanowicz, K.; Hanuza, J.

    2010-01-01

    Graphical abstract: New organic-organic salt, 2-amino-4-methyl-3-nitropyridinium trifluoroacetate, has been synthesised and characterised by FT-IR, FT-Raman, DSC and single crystal X-ray crystallography. The 2-amino-4-methyl-3-nitropyridinium trifluoroacetate undergoes a reversible phase transition at ∼162 K. The X-ray structures, vibrational spectra and quantum chemical DFT calculations (B3LYP/6-31G(d,p) approach) have been analysed for high-temperature and low-temperature modifications of the compound, which both crystallize in orthorhombic space group Pbca with two non-equivalent cations and two anions in the asymmetric unit. Their crystal and molecular structures have been compared and the role of the intermolecular interactions in these crystals has been analysed. The mechanisms of the phase transition have been proposed. - Abstract: New organic-organic salt, 2-amino-4-methyl-3-nitropyridinium trifluoroacetate, has been synthesised and characterised by FT-IR, FT-Raman, DSC and single crystal X-ray crystallography. The 2-amino-4-methyl-3-nitropyridinium trifluoroacetate undergoes a reversible phase transition at ∼162 K. The X-ray structures, vibrational spectra and quantum chemical DFT calculations (B3LYP/6-31G(d,p) approach) have been analysed for high-temperature and low-temperature modifications of the compound, which both crystallize in orthorhombic space group Pbca with two non-equivalent cations and two anions in the asymmetric unit. Their crystal and molecular structures have been compared and the role of the intermolecular interactions in these crystals has been analysed. The mechanisms of the phase transition have been proposed.

  16. Order-disorder phase transitions and their influence on the structure and vibrational properties of new hybrid material: 2-Amino-4-methyl-3-nitropyridinium trifluoroacetate

    Energy Technology Data Exchange (ETDEWEB)

    Lorenc, J., E-mail: jadwiga.lorenc@ue.wroc.pl [Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economy, University of Economic, Wroclaw (Poland); Bryndal, I. [Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economy, University of Economic, Wroclaw (Poland); Faculty of Chemistry, University of Wroclaw (Poland); Syska, W.; Wandas, M. [Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economy, University of Economic, Wroclaw (Poland); Marchewka, M.; Pietraszko, A. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw (Poland); Lis, T. [Faculty of Chemistry, University of Wroclaw (Poland); Maczka, M.; Hermanowicz, K. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw (Poland); Hanuza, J. [Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economy, University of Economic, Wroclaw (Poland); Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw (Poland)

    2010-08-23

    Graphical abstract: New organic-organic salt, 2-amino-4-methyl-3-nitropyridinium trifluoroacetate, has been synthesised and characterised by FT-IR, FT-Raman, DSC and single crystal X-ray crystallography. The 2-amino-4-methyl-3-nitropyridinium trifluoroacetate undergoes a reversible phase transition at {approx}162 K. The X-ray structures, vibrational spectra and quantum chemical DFT calculations (B3LYP/6-31G(d,p) approach) have been analysed for high-temperature and low-temperature modifications of the compound, which both crystallize in orthorhombic space group Pbca with two non-equivalent cations and two anions in the asymmetric unit. Their crystal and molecular structures have been compared and the role of the intermolecular interactions in these crystals has been analysed. The mechanisms of the phase transition have been proposed. - Abstract: New organic-organic salt, 2-amino-4-methyl-3-nitropyridinium trifluoroacetate, has been synthesised and characterised by FT-IR, FT-Raman, DSC and single crystal X-ray crystallography. The 2-amino-4-methyl-3-nitropyridinium trifluoroacetate undergoes a reversible phase transition at {approx}162 K. The X-ray structures, vibrational spectra and quantum chemical DFT calculations (B3LYP/6-31G(d,p) approach) have been analysed for high-temperature and low-temperature modifications of the compound, which both crystallize in orthorhombic space group Pbca with two non-equivalent cations and two anions in the asymmetric unit. Their crystal and molecular structures have been compared and the role of the intermolecular interactions in these crystals has been analysed. The mechanisms of the phase transition have been proposed.

  17. On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small water clusters: Benchmarks approaching the complete basis set limit

    Science.gov (United States)

    Santra, Biswajit; Michaelides, Angelos; Scheffler, Matthias

    2007-11-01

    The ability of several density-functional theory (DFT) exchange-correlation functionals to describe hydrogen bonds in small water clusters (dimer to pentamer) in their global minimum energy structures is evaluated with reference to second order Møller-Plesset perturbation theory (MP2). Errors from basis set incompleteness have been minimized in both the MP2 reference data and the DFT calculations, thus enabling a consistent systematic evaluation of the true performance of the tested functionals. Among all the functionals considered, the hybrid X3LYP and PBE0 functionals offer the best performance and among the nonhybrid generalized gradient approximation functionals, mPWLYP and PBE1W perform best. The popular BLYP and B3LYP functionals consistently underbind and PBE and PW91 display rather variable performance with cluster size.

  18. Comparison of HfCl4, HfI4, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO2 films deposited by ALD: A DFT study

    Science.gov (United States)

    Cortez-Valadez, M.; Fierro, C.; Farias-Mancilla, J. R.; Vargas-Ortiz, A.; Flores-Acosta, M.; Ramírez-Bon, R.; Enriquez-Carrejo, J. L.; Soubervielle-Montalvo, C.; Mani-Gonzalez, P. G.

    2016-06-01

    The final structure of HfO2 films grown by atomic layer deposition (ALD) after reaction with OH- ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl4 (hafnium tetrachloride), HfI4 (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO-H was studied employing the B3LYP (Becke 3-parameter, Lee-Yang-Parr) hybrid functional and the PBE (Perdew-Burke-Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  19. Gaussian-3 theory using density functional geometries and zero-point energies

    International Nuclear Information System (INIS)

    Baboul, A.G.; Curtiss, L.A.; Redfern, P.C.; Raghavachari, K.

    1999-01-01

    A variation of Gaussian-3 (G3) theory is presented in which the geometries and zero-point energies are obtained from B3LYP density functional theory [B3LYP/6-31G(d)] instead of geometries from second-order perturbation theory [MP2(FU)/6-31G(d)] and zero-point energies from Hartree - Fock theory [HF/6-31G(d)]. This variation, referred to as G3//B3LYP, is assessed on 299 energies (enthalpies of formation, ionization potentials, electron affinities, proton affinities) from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The G3//B3LYP average absolute deviation from experiment for the 299 energies is 0.99 kcal/mol compared to 1.01 kcal/mol for G3 theory. Generally, the results from the two methods are similar, with some exceptions. G3//B3LYP theory gives significantly improved results for several cases for which MP2 theory is deficient for optimized geometries, such as CN and O 2 + . However, G3//B3LYP does poorly for ionization potentials that involve a Jahn - Teller distortion in the cation (CH 4 + , BF 3 + , BCl 3 + ) because of the B3LYP/6-31G(d) geometries. The G3(MP2) method is also modified to use B3LYP/6-31G(d) geometries and zero-point energies. This variation, referred to as G3(MP2)//B3LYP, has an average absolute deviation of 1.25 kcal/mol compared to 1.30 kcal/mol for G3(MP2) theory. Thus, use of density functional geometries and zero-point energies in G3 and G3(MP2) theories is a useful alternative to MP2 geometries and HF zero-point energies. copyright 1999 American Institute of Physics

  20. The direct hydroxylation of benzene to phenol catalyzed by Fe-ZSM-5 zeolite : a DFT and hybrid MP2:DFT calculation

    NARCIS (Netherlands)

    Yang, Z.; Yang, G.; Liu, X.; Han, Xiuwen

    2013-01-01

    The title reactions over Fe-III and Fe-II-ZSM-5 zeolites are divided into seven and six steps, wherein the M06L:B3LYP energy barriers of N2O decomposition to form active site, benzene activation to form C-O bond and proton transfer to form phenol are equal to 37.0, 13.7, 17.2 and 33.7, 3.0, 19.1

  1. DFT calculations of the structures and vibrational spectra of the [Fe(bpy)3]2+ and [Ru(bpy)3]2+ complexes

    International Nuclear Information System (INIS)

    Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

    2008-01-01

    Structures of the [M(bpy) 3 ] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3 ] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1 E MLCT excited state

  2. DFT calculations of the structures and vibrational spectra of the [Fe(bpy) 3] 2+ and [Ru(bpy) 3] 2+ complexes

    Science.gov (United States)

    Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

    2008-09-01

    Structures of the [M(bpy) 3] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1E MLCT excited state.

  3. Comparison of HfCl{sub 4}, HfI{sub 4}, TEMA-Hf, and TDMA-Hf as precursors in early growing stages of HfO{sub 2} films deposited by ALD: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Cortez-Valadez, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Fierro, C.; Farias-Mancilla, J.R. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); Vargas-Ortiz, A. [Universidad Autónoma de Sinaloa, Facultad de Ingeniería Mochis, Ciudad Universitaria, C.P. 81223 Los Mochis, Sinaloa (Mexico); Flores-Acosta, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Ramírez-Bon, R. [Centro de Investigación y Estudios Avanzados del IPN, Unidad Querétaro, Apdo. Postal 1-798, 76001 Querétaro, Qro. (Mexico); Enriquez-Carrejo, J.L. [Instituto de Ingeniería y Tecnología, Departamento de Física y Matemáticas, Universidad Autónoma de Ciudad Juárez, Av. del Charro 450, Cd. Juárez C.P. 32310, Chihuahua (Mexico); and others

    2016-06-15

    Highlights: • Hafnium oxide growth on Si(100) by atomic layer deposition was simulated. • The interface structure was considered as silicate and silicide. • The interface was studied employing DFT. • TDMA-Hf precursor show better interface stability. - Abstract: The final structure of HfO{sub 2} films grown by atomic layer deposition (ALD) after reaction with OH{sup −} ions has been analyzed by DFT (density functional theory). The interaction of the precursors: HfCl{sub 4} (hafnium tetrachloride), HfI{sub 4} (hafnium tetraiodide), TEMA-Hf (tetrakis-ethylmethylamino hafnium), and TDMA-Hf (tetrakis-dimethylamino hafnium) with HO–H was studied employing the B3LYP (Becke 3-parameter, Lee–Yang–Parr) hybrid functional and the PBE (Perdew–Burke–Ernzerhof) generalized gradient functional. The structural evolution at the Si(100) surface has been analyzed by LDA (local density approximation). The structural parameters: bond length and bond angle, and the vibrational parameters for the optimized structures are also reported. The presence of hafnium silicate at the interface was detected. The infrared spectra and structural parameters obtained in this work agree with previously reported experimental results.

  4. Monothiodibenzoylmethane: Structural and vibrational assignments

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Gorski, Alexander; Posokhov, Yevgen

    2007-01-01

    vibrational spectra were compared with theoretical transitions obtained with B3LYP/cc-pVTZ density functional theory (DFT). The results leave no doubt that the stable ground state configuration of TDBM corresponds to the intramolecularly hydrogen bonded enol form (e-CCC), and that the photoproduct corresponds...

  5. A combined Raman spectroscopic and theoretical investigation of fundamental vibrational bands of furfuryl alcohol (2-furanmethanol)

    DEFF Research Database (Denmark)

    Barsberg, S.; Berg, Rolf W.

    2006-01-01

    . study of FA in weakly interacting environments. It is the first study of FA vibrational properties based on d. functional theory (DFT/B3LYP), and a recently proposed hybrid approach to the calcn. of fundamental frequencies, which also includes an anharmonic contribution. FA occupies five different...

  6. Conformational determination of [Leu]enkephalin based on theoretical and experimental VA and VCD spectral analyses

    DEFF Research Database (Denmark)

    Abdali, Salim; Jalkanen, Karl J.; Cao, X.

    2004-01-01

    Conformational determination of [Leu]enkephalin in DMSO-d6 is carried out using VA and VCD spectral analyses. Conformational energies, vibrational frequencies and VA and VCD intensities are calculated using DFT at B3LYP/6-31G* level of theory. Comparison between the measured spectra...

  7. The vibrational structure of dibenzo-p-dioxin

    DEFF Research Database (Denmark)

    Eriksen, Troels Kongsgaard; Hansen, Bjarke Knud Vilster; Spanget-Larsen, Jens

    2008-01-01

    by the results of a harmonic analysis based on B3LYP/cc-pVTZ density functional theory (DFT). The combined experimental and theoretical results led to proposal of a nearly complete assignment of the fundamental vibrational transitions of DD, involving reassignment of several transitions. The results...

  8. Assignment of phantom bands in the solid-state infrared and Raman spectra of coronene: the importance of a minute out-of-plane distortion

    NARCIS (Netherlands)

    Todorov, P.D.; Jenneskens, L.W.; van Lenthe, J.H.

    2010-01-01

    The molecular geometry and the normal modes properties of coronene are investigated by means of DFT B3LYP and restricted/Hartree–Fock calculations utilizing basis sets of triple zeta +polarization quality. The interpretation of the infrared and Raman spectra of coronene, especially in solid state,

  9. Evolution of the bonding mechanism of ZnO under isotropic compression: A first-principles study

    International Nuclear Information System (INIS)

    Zhou, G.C.; Sun, L.Z.; Wang, J.B.; Zhong, X.L.; Zhou, Y.C.

    2008-01-01

    The electronic structure and the bonding mechanism of ZnO under isotropic pressure have been studied by using the full-potential linear augmented plane wave (FP-LAPW) method within the density-functional theory (DFT) based on LDA+U exchange correlation (EXC) potential. We used the theory of Atoms in Molecules (AIM) method to analyze the change of the charge transfer and the bonding strength under isotropic pressure. The results of the theoretical analysis show that charge transfer between Zn and O atomic basins nearly linearly increases with the increasing pressure. Charge density along the Zn-O bond increases under the high pressure. The bonding strength and the ionicity of Zn-O bond also increase with the increasing pressure. The linear evolution process of the bonding mechanism under isotropic pressure was shown clearly in the present paper

  10. Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

    International Nuclear Information System (INIS)

    Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit; Chowdhury, Joydeep; Ganguly, Tapan

    2010-01-01

    UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (ε S ∼10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (ε S ∼37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

  11. Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

    Energy Technology Data Exchange (ETDEWEB)

    Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India); Chowdhury, Joydeep [Sammilani Mahavidyalaya Baghajatin Station, West Bengal (India); Ganguly, Tapan, E-mail: sptg@mahendra.iacs.res.i [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India)

    2010-06-15

    UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (epsilon{sub S}approx10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (epsilon{sub S}approx37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

  12. Molecular structure, vibrational spectra and DFT computational studies of melaminium N-acetylglycinate dihydrate

    Science.gov (United States)

    Tanak, H.; Pawlus, K.; Marchewka, M. K.

    2016-10-01

    Melaminium N-acetylglycinate dihydrate, an organic material has been synthesized and characterized by X-ray diffraction, FT-IR, and FT-Raman spectroscopies for the protiated and deuteriated crystals. The title complex crystallizes in the triclinic system, and the space group is P-1 with a = 5.642(1) Å, b = 7.773(2) Å, c = 15.775(3) Å, α = 77.28(1)°, β = 84.00(1)°, γ = 73.43(1)° and Z = 2. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional method (B3LYP) with the 6-311++G(d,p) basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. The intermolecular hydrogen bonding interactions of the title compound have been investigated using the natural bonding orbital analysis. It reveals that the O-H···O, N-H···N and N-H···O intermolecular interactions significantly influence crystal packing of this molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, thermodynamic properties, frontier orbitals and chemical reactivity descriptors were also performed at 6-311++G(d,p) level of theory.

  13. Experimental spectroscopic (FTIR, FT-Raman, FT-NMR, UV-Visible) and DFT studies of 1-ethyl-1,4-dihydro-7-methyl-4oxo-1,8 napthyridine-3-carboxylic acids.

    Science.gov (United States)

    Muthu, S; Elamurugu Porchelvi, E

    2013-12-01

    The solid phase FTIR and FT-Raman spectra of 1-ethyl-1,4-dihydro-7-methyl-4oxo-1,8 napthyridine-3-carboxylic acid (EDMONCA) have been recorded in the regions 4000-500 and 4000-400 cm(-1) respectively. The equilibrium geometry, harmonic vibrational frequencies have been investigated by DFT/B3LYP and B3PW91 methods with 6-311G (d,p) basis set. The different between the observed and scaled wave number values of most of the fundamental is very small. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFFM). Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-Visible spectrum of the compound was recorded and the electronic properties HOMO and LOMO energies were measured. The electric dipole moment (μD) and first hyperpolarizability (βtot) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the EDMONCA molecule may have microscopic nonlinear optics (NLO) behavior with non-zero values. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shift of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. Thermal stability of EDMONCA was studied by thermogravimetric analysis (TGA). Next Fukui function was calculated to explain the chemical selectivity or reactivity site in EDMONCA. Finally molecular electrostatic potential (MEP) and other molecular properties were performed. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Molecular conformational analysis, vibrational spectra and normal coordinate analysis of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene based on density functional theory calculations.

    Science.gov (United States)

    Joseph, Lynnette; Sajan, D; Chaitanya, K; Isac, Jayakumary

    2014-03-25

    The conformational behavior and structural stability of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene (TDBE) were investigated by using density functional theory (DFT) method with the B3LYP/6-311++G(d,p) basis set combination. The vibrational wavenumbers of TDBE were computed at DFT level and complete vibrational assignments were made on the basis of normal coordinate analysis calculations (NCA). The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compound. The infrared and Raman spectra were also predicted from the calculated intensities. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Communication: Hole localization in Al-doped quartz SiO{sub 2} within ab initio hybrid-functional DFT

    Energy Technology Data Exchange (ETDEWEB)

    Gerosa, Matteo [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Di Valentin, Cristiana; Pacchioni, Gianfranco [Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, via R. Cozzi 55, 20125 Milan (Italy); Bottani, Carlo Enrico, E-mail: carlo.bottani@polimi.it [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Center for Nano Science and Technology @Polimi, Istituto Italiano di Tecnologia, via Pascoli 70/3, 20133 Milano (Italy); Onida, Giovanni [Dipartimento di Fisica dell’ Universita’ degli Studi di Milano and European Theoretical Spectroscopy Facility (ETSF), Via Celoria 16, 20133 Milan (Italy)

    2015-09-21

    We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO{sub 2}, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators.

  16. Structure and electronic properties of azadirachtin.

    Science.gov (United States)

    de Castro, Elton A S; de Oliveira, Daniel A B; Farias, Sergio A S; Gargano, Ricardo; Martins, João B L

    2014-02-01

    We performed a combined DFT and Monte Carlo (13)C NMR chemical-shift study of azadirachtin A, a triterpenoid that acts as a natural insect antifeedant. A conformational search using a Monte Carlo technique based on the RM1 semiempirical method was carried out in order to establish its preferred structure. The B3LYP/6-311++G(d,p), wB97XD/6-311++G(d,p), M06/6-311++G(d,p), M06-2X/6-311++G(d,p), and CAM-B3LYP/6-311++G(d,p) levels of theory were used to predict NMR chemical shifts. A Monte Carlo population-weighted average spectrum was produced based on the predicted Boltzmann contributions. In general, good agreement between experimental and theoretical data was obtained using both methods, and the (13)C NMR chemical shifts were predicted highly accurately. The geometry was optimized at the semiempirical level and used to calculate the NMR chemical shifts at the DFT level, and these shifts showed only minor deviations from those obtained following structural optimization at the DFT level, and incurred a much lower computational cost. The theoretical ultraviolet spectrum showed a maximum absorption peak that was mainly contributed by the tiglate group.

  17. Computational investigation of rearrangements in huisgen cycloadducts of azolium N-dicyanomethanide 1,3-dipoles with alkynes: a mechanistic panoply.

    Science.gov (United States)

    Burke, Luke A; Butler, Richard N

    2009-08-07

    The reaction surfaces leading to rearrangements and ring expansions of azapentalene cycloadducts of imidazolo- and triazolodicyanomethanide 1,3-dipoles with alkynes are studied with the B3LYP DFT method using the 6-31G(d) and 6-311+G(2d,p) basis sets. The surprisingly complex surface involves (1) consecutive but not combined pericyclic steps, a coarctate TS, and pseudopericyclic mechanisms, (2) anchimerically assisted H-atom transfer competing effectively with concerted symmetry-allowed sigmatropic steps, and (3) azolium methanide zwitterions and ketenimines as key intermediates. The azolium methanide is identified as the intermediate detected previously in a variable-temperature NMR experiment that converted the unstable cycloadduct to product imine.

  18. Accurate prediction of the enthalpies of formation for xanthophylls.

    Science.gov (United States)

    Lii, Jenn-Huei; Liao, Fu-Xing; Hu, Ching-Han

    2011-11-30

    This study investigates the applications of computational approaches in the prediction of enthalpies of formation (ΔH(f)) for C-, H-, and O-containing compounds. Molecular mechanics (MM4) molecular mechanics method, density functional theory (DFT) combined with the atomic equivalent (AE) and group equivalent (GE) schemes, and DFT-based correlation corrected atomization (CCAZ) were used. We emphasized on the application to xanthophylls, C-, H-, and O-containing carotenoids which consist of ∼ 100 atoms and extended π-delocaization systems. Within the training set, MM4 predictions are more accurate than those obtained using AE and GE; however a systematic underestimation was observed in the extended systems. ΔH(f) for the training set molecules predicted by CCAZ combined with DFT are in very good agreement with the G3 results. The average absolute deviations (AADs) of CCAZ combined with B3LYP and MPWB1K are 0.38 and 0.53 kcal/mol compared with the G3 data, and are 0.74 and 0.69 kcal/mol compared with the available experimental data, respectively. Consistency of the CCAZ approach for the selected xanthophylls is revealed by the AAD of 2.68 kcal/mol between B3LYP-CCAZ and MPWB1K-CCAZ. Copyright © 2011 Wiley Periodicals, Inc.

  19. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    In the present work, a conformational analysis of 3-Hydroxy-propeneselenal is performed using several computational methods, including HF, DFT (B3LYP), and G2MP2 levels of theory. The relative ... The conformational preference of this molecule was found to be mainly determined by the formation of Se…H-O and ...

  20. Vibrational spectroscopic study and NBO analysis on tranexamic acid using DFT method

    Science.gov (United States)

    Muthu, S.; Prabhakaran, A.

    2014-08-01

    In this work, we reported the vibrational spectra of tranexamic acid (TA) by experimental and quantum chemical calculation. The solid phase FT-Raman and FT-IR spectra of the title compound were recorded in the region 4000 cm-1 to 100 cm-1 and 4000 cm-1 to 400 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of TA in the ground state have been calculated by using density functional theory (DFT) B3LYP method with standard 6-31G(d,p) basis set. The scaled theoretical wavenumber showed very good agreement with the experimental values. The vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that ED in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electrostatic potential mapped onto an isodensity surface has been obtained. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase.

  1. A 3D printed dual GSM band near isotropic on-package antenna

    KAUST Repository

    Zhen, Su

    2017-10-25

    In this paper, we propose an on-package dual band monopole antenna with near-isotropic radiation pattern for GSM mobile applications. The proposed antenna is well matched for both GSM 900 and 1800 bands and provides decent gain for both the bands (1.67 and 3.27 dBi at 900 MHz and 1800 MHz respectively). The antenna is printed with silver ink on a 3D printed polymer based package. The package houses the GSM electronics and the battery. By optimizing the antenna arms width and length, a near-isotropic radiation pattern is achieved. Unlike the published isotropic antennas which are either single band or large in size, the proposed antenna covers both GSM bands with required bandwidth and is only half wavelength long. The design is low cost and highly suitable for various GSM applications such as localization, in additional to conventional communication applications.

  2. The ground states of iron(III) porphines: role of entropy-enthalpy compensation, Fermi correlation, dispersion, and zero-point energies.

    Science.gov (United States)

    Kepp, Kasper P

    2011-10-01

    Porphyrins are much studied due to their biochemical relevance and many applications. The density functional TPSSh has previously accurately described the energy of close-lying electronic states of transition metal systems such as porphyrins. However, a recent study questioned this conclusion based on calculations of five iron(III) porphines. Here, we compute the geometries of 80 different electronic configurations and the free energies of the most stable configurations with the functionals TPSSh, TPSS, and B3LYP. Zero-point energies and entropy favor high-spin by ~4kJ/mol and 0-10kJ/mol, respectively. When these effects are included, and all electronic configurations are evaluated, TPSSh correctly predicts the spin of all the four difficult phenylporphine cases and is within the lower bound of uncertainty of any known theoretical method for the fifth, iron(III) chloroporphine. Dispersion computed with DFT-D3 favors low-spin by 3-53kJ/mol (TPSSh) or 4-15kJ/mol (B3LYP) due to the attractive r(-6) term and the shorter distances in low-spin. The very large and diverse corrections from TPSS and TPSSh seem less consistent with the similarity of the systems than when calculated from B3LYP. If the functional-specific corrections are used, B3LYP and TPSSh are of equal accuracy, and TPSS is much worse, whereas if the physically reasonable B3LYP-computed dispersion effect is used for all functionals, TPSSh is accurate for all systems. B3LYP is significantly more accurate when dispersion is added, confirming previous results. Copyright © 2011 Elsevier Inc. All rights reserved.

  3. Synthesis, structural and vibrational investigation on 2-phenyl-N-(pyrazin-2-yl)acetamide combining XRD diffraction, FT-IR and NMR spectroscopies with DFT calculations.

    Science.gov (United States)

    Lukose, Jilu; Yohannan Panicker, C; Nayak, Prakash S; Narayana, B; Sarojini, B K; Van Alsenoy, C; Al-Saadi, Abdulaziz A

    2015-01-25

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-phenyl-N-(pyrazin-2-yl)acetamide have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized by using the HF/6-31G(6D,7F) and B3LYP/6-31G(6D,7F) calculations. The geometrical parameters are in agreement with the XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Gauge-including atomic orbital (1)H-NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. First hyperpolarizability is calculated in order to find its role in non linear optics. From the XRD data, in the crystal, molecules are held together by strong C-H⋯O and N-H⋯O intermolecular interactions. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Evaluating interaction energies of weakly bonded systems using the Buckingham-Hirshfeld method

    Science.gov (United States)

    Krishtal, A.; Van Alsenoy, C.; Geerlings, P.

    2014-05-01

    We present the finalized Buckingham-Hirshfeld method (BHD-DFT) for the evaluation of interaction energies of non-bonded dimers with Density Functional Theory (DFT). In the method, dispersion energies are evaluated from static multipole polarizabilities, obtained on-the-fly from Coupled Perturbed Kohn-Sham calculations and partitioned into diatomic contributions using the iterative Hirshfeld partitioning method. The dispersion energy expression is distributed over four atoms and has therefore a higher delocalized character compared to the standard pairwise expressions. Additionally, full multipolar polarizability tensors are used as opposed to effective polarizabilities, allowing to retain the anisotropic character at no additional computational cost. A density dependent damping function for the BLYP, PBE, BP86, B3LYP, and PBE0 functionals has been implemented, containing two global parameters which were fitted to interaction energies and geometries of a selected number of dimers using a bi-variate RMS fit. The method is benchmarked against the S22 and S66 data sets for equilibrium geometries and the S22x5 and S66x8 data sets for interaction energies around the equilibrium geometry. Best results are achieved using the B3LYP functional with mean average deviation values of 0.30 and 0.24 kcal/mol for the S22 and S66 data sets, respectively. This situates the BHD-DFT method among the best performing dispersion inclusive DFT methods. Effect of counterpoise correction on DFT energies is discussed.

  5. X-ray, MP2 and DFT studies of the structure and vibrational spectra of trigonellinium chloride

    International Nuclear Information System (INIS)

    Szafran, M.; Koput, J.; Dega-Szafran, Z.; Katrusiak, A.; Pankowski, M.; Stobiecka, K.

    2003-01-01

    The effects of hydrogen bonding, inter- and intramolecular electrostatic interactions on the conformation of trigonellinium chloride, TRGH...Cl, in the crystal and on that of a single molecule have been studied by X-ray diffraction, FT-IR, Raman, 1 H and 13 C NMR spectroscopies, and by MP2 and DFT calculations. In the crystal, the Cl - anion is connected with protonated trigonelline via hydrogen bond, O-H...Cl - =2.915(3) Angst, and three N + ...Cl - intermolecular electrostatic interactions. In a single molecule, the Cl - anion is also engaged in a slightly longer hydrogen bond, O-H...Cl - =2.948-3.019 Angst, but only in one type of intramolecular electrostatic interaction. The optimized bond lengths and bond angles at the MP2 and B3LYP levels of theory are in good agreement with the X-ray data, except conformation of the COOH group, which is cis (syn) in the crystal and trans (anti) in the single molecule. The probable assignments for the experimental solid state vibrational spectra of TRGH.Cl and TRGD.Cl based on the calculated MP2/cc-pVDZ frequencies and intensities were made. The effect of quaternization of nicotinic acid, its salt and amide on chemical shifts of the ring protons and carbons is analyzed

  6. Initial experience with 3D isotropic high-resolution 3 T MR arthrography of the wrist.

    Science.gov (United States)

    Sutherland, John K; Nozaki, Taiki; Kaneko, Yasuhito; J Yu, Hon; Rafijah, Gregory; Hitt, David; Yoshioka, Hiroshi

    2016-01-16

    Our study was performed to evaluate the image quality of 3 T MR wrist arthrograms with attention to ulnar wrist structures, comparing image quality of isotropic 3D proton density fat suppressed turbo spin echo (PDFS TSE) sequence versus standard 2D 3 T sequences as well as comparison with 1.5 T MR arthrograms. Eleven consecutive 3 T MR wrist arthrograms were performed and the following sequences evaluated: 3D isotropic PDFS, repetition time/echo time (TR/TE) 1400/28.3 ms, voxel size 0.35x0.35x0.35 mm, acquisition time 5 min; 2D coronal sequences with slice thickness 2 mm: T1 fat suppressed turbo spin echo (T1FS TSE) (TR/TE 600/20 ms); proton density (PD) TSE (TR/TE 3499/27 ms). A 1.5 T group of 18 studies with standard sequences were evaluated for comparison. All MR imaging followed fluoroscopically guided intra-articular injection of dilute gadolinium contrast. Qualitative assessment related to delineation of anatomic structures between 1.5 T and 3 T MR arthrograms was carried out using Mann-Whitney test and the differences in delineation of anatomic structures among each sequence in 3 T group were analyzed with Wilcoxon signed-rank test. Quantitative assessment of mean relative signal intensity (SI) and relative contrast measurements was performed using Wilcoxon signed-rank test. Mean qualitative scores for 3 T sequences were significantly higher than 1.5 T (p < 0.01), with isotropic 3D PDFS sequence having highest mean qualitative scores (p < 0.05). Quantitative analysis demonstrated no significant difference in relative signal intensity among the 3 T sequences. Significant differences were found in relative contrast between fluid-bone and fluid-fat comparing 3D and 2D PDFS (p < 0.01). 3D isotropic PDFS sequence showed promise in both qualitative and quantitative assessment, suggesting this may be useful for MR wrist arthrograms at 3 T. Primary reasons for diagnostic potential include the ability to make reformations in any

  7. The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study

    DEFF Research Database (Denmark)

    Fristrup, Peter; Kreis, Michael; Palmelund, Anders

    2008-01-01

    that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement...

  8. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane

    DEFF Research Database (Denmark)

    Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.

    2014-01-01

    assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl...

  9. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    The structure of the title molecule has been optimized and the structural parameters have been calculated by DFT/B3LYP method with 6-311++G(d,p) basis set. The fundamental vibrational wavenumbers as well as their intensities were calculated and excellent agreement between observed and calculated wavenumbers ...

  10. NMR Analysis of Some Pentacycloundecanedione Derivatives ...

    African Journals Online (AJOL)

    Nuclear Overhauser Effect Spectroscopy (NOESY) interaction between the two nonequivalent bridge protons and protons on the cage skeleton proved to be a very convenient handle to elucidate the structures of the PCU compounds. A density functional theory (DFT) optimization [B3LYP/6-31+G(d)] of two possible ketal ...

  11. Pramana – Journal of Physics | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    The theoretical parameters of the transparent conducting metal oxides were calculated using DFT/B3LYP/LANL2DZ method. The optimised bond parameters such as bond lengths, bond angles and dihedral angles were calculated using the same theory. The non-linear optical property of the title compound was calculated ...

  12. DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

    Science.gov (United States)

    Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

    2018-05-01

    The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

  13. DFT/GIAO calculations of the relative contributions of hyperconjugation to the chemical shifts of ethanol

    International Nuclear Information System (INIS)

    Carneiro, J. Walkimar de M.; Dias, Jacques F.; Seidl, Peter R.; Tostes, J. Glauco R.

    2002-01-01

    Our previous DFT/GIAO calculations on different types of alcohols reveal that the rotation of the hydroxyl group can affect the chemical shift of carbons and hydrogens close to the substituent in different ways. Besides the steric and electrostatic effects that have been widely studied, hyperconjugation with the lone pairs on oxygen of the hydroxyl group leads to changes in bond lengths and angles as well as to different charge distributions. As all three of these factors also affect chemical shifts, we undertook a systematic investigation of their relative contributions to the chemical shifts of ethanol, a molecule in which there is minimum interference among these factors. Calculations by the B3LYP method at the 6-31G(d) level for ethanol conformers corresponding to a rotation around the carbon-oxygen bond at 30 dec increments are used to show how relative contributions vary with the dihedral angle formed between the carbon-carbon and oxygen-hydrogen bonds (C-C-O-H). Largest contributions to carbon chemical shifts can be attributed to changes in bond lengths while for hydrogen chemical shifts also contribute significantly differences in charge distribution. (author)

  14. Estimation of ground and excited-state dipole moments of 1, 2-diazines by solvatochromic method and quantum-chemical calculation

    DEFF Research Database (Denmark)

    Manohara, S.R.; Kumar, V. Udaya; Shivakumaraiah

    2013-01-01

    chemical calculations using the DFT method by adopting B3LYP/6-31G* level of theory (Gaussian 03) and using the AM1 method (Chem3D Ultra 8.0). It was observed that, dipole moments of diazines in the excited-state (μe) were greater than the corresponding ground-state values (μg), indicating a substantial...

  15. Spectroscopic studies (FTIR, FT-Raman and UV-Visible), normal coordinate analysis, NBO analysis, first order hyper polarizability, HOMO and LUMO analysis of (1R)-N-(Prop-2-yn-1-yl)-2,3-dihydro-1H-inden-1-amine molecule by ab initio HF and density functional methods.

    Science.gov (United States)

    Muthu, S; Ramachandran, G

    2014-01-01

    The Fourier transform infrared (FT-IR) and FT-Raman of (1R)-N-(Prop-2-yn-1-yl)-2,3-dihydro-1H-inden-1-amine (1RNPDA) were recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1) respectively. A complete assignment and analysis of the fundamental vibrational modes of the molecule were carried out. The observed fundamental modes have been compared with the harmonic vibrational frequencies computed using HF method by employing 6-31G(d,p) basis set and DFT(B3LYP) method by employing 6-31G(d,p) basis set. The vibrational studies were interpreted in terms of Potential Energy Distribution (PED). The complete vibrational frequency assignments were made by Normal Co-ordinate Analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The first order hyper polarizability (β0) of this molecular system and related properties (α, μ, and Δα) are calculated using B3LYP/6-31G(d,p) method based on the finite-field approach. The thermodynamic functions of the title compound were also performed at the above methods and basis set. A detailed interpretation of the infrared and Raman spectra of 1RNPDA is reported. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated using the GIAO method confirms with the experimental values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using Natural Bond Orbital (NBO) analysis. UV-vis spectrum of the compound was recorded and electronic properties such as excitation energies, oscillator strength and wavelength were performed by TD-DFT/B3LYP using 6-31G(d,p) basis set. The HOMO and LUMO energy gap reveals that the energy gap reflects the chemical activity of the molecule. The observed and calculated wave numbers are formed to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed spectra. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Spectroscopic (vibrational, NMR and UV-vis.) and quantum chemical investigations on 4-hexyloxy-3-methoxybenzaldehyde.

    Science.gov (United States)

    Abbas, Ashgar; Gökce, Halil; Bahçeli, Semiha

    2016-01-05

    In this study, the 4-hexyloxy-3-methoxybenzaldehyde compound as one of the derivatives of vanillin which is a well known flavoring agent, C14H20O3, has been investigated by experimentally and extensively utilizing density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In this context, the optimized geometry, vibrational frequencies, (1)H and (13)C NMR chemical shifts, UV-vis. (in gas phase and in methanol solvent) spectra, HOMO-LUMO analysis, molecular electrostatic potential (MEP), thermodynamic parameters and atomic charges of 4-hexyloxy-3-methoxybenzaldehyde have been calculated. In addition, theoretically predicted IR, Raman and UV-vis. (in gas phase and in methanol solvent) spectra of the mentioned molecule have been constructed. The results calculated were compared with the experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Experimental demonstration of improved fiber nonlinearity tolerance for unique-word DFT-spread OFDM systems.

    Science.gov (United States)

    Chen, Xi; Li, An; Gao, Guanjun; Shieh, William

    2011-12-19

    In this paper we experimentally demonstrate transmission performance of optical DFT-spread OFDM systems in comparison with conventional OFDM systems. A 440.8-Gb/s superchannel consisting of 8 x 55.1-Gb/s densely-spaced DFT-S OFDM signal is successfully received after 1120-km transmission with a spectral efficiency of 3.5 b/s/Hz. It is shown that DFT-S OFDM can achieve an improvement of 1 dB in Q factor and 1 dB in launch power over conventional OFDM. Additionally, unique word aided phase estimation algorithm is proposed and demonstrated enabling extremely long OFDM symbol transmission.

  18. Radical scavenging activity of some natural tropolones by density functional theory

    Directory of Open Access Journals (Sweden)

    A. G. Al-Sehemi

    2017-07-01

    Full Text Available The ground state neutral geometries of some natural tropolones, i.e. stipitatonic acid (AF1, stipitalide (AF2, stipitaldehydic acid (AF3 and methyl stipitate (AF4 have been optimized by using Density Functional Theory (DFT at B3LYP/6-31G*, B3LYP/6-31G**, B3LYP/6-31+G* and B3LYP/6-31+G** levels of theory. The excited state geometries of AF1-AF4 were optimized by adopting the Time Dependent Density Functional Theory (TDDFT at the same levels of theory. The frequencies and cation species of AF1-AF4 were also computed at all the above mentioned levels of theory. We shed light on the electro-optical and molecular properties, e.g. energy gaps, highest occupied molecular orbitals, lowest unoccupied molecular orbitals, absorption wavelengths, electronegativity (χ, hardness (η, electrophilicity (ω, softness (S, electrophilicity index (ωi and the radical scavenging activity (RSA. Hydrogen atom transfer (HAT and one-electron transfer mechanisms have been discussed to shed light on the RSA. The smallest ionization potential and bond dissociation energy of AF4 are revealing that this compound would have more RSA than those of other counterparts.

  19. MOLECULAR STRUCTURE AND VIBRATIONAL FREQUENCIES OF

    Directory of Open Access Journals (Sweden)

    Fatih UCUN

    2009-02-01

    Full Text Available Abstract: The molecular structure, vibrational frequencies and the corresponding assignments of N-aminophthalimide (NAPH in the ground state have been calculated using the Hartree-Fock (HF and density functional methods (B3LYP with 6-31G (d, p basis set. The calculations were utilized in the CS symmetry of NAPH. The obtained vibrational frequencies and optimized geometric parameters (bond lengths and bond angles were seen to be in good agreement with the experimental data. The comparison of the observed and calculated results showed that B3LYP is superior to the scaled HF method. Theoretical infrared intensities and Raman activities were also reported. Key words: N-aminophthalimide; vibrations; IR spectra; Raman spectra; HF; DFT N-AMİNOFİTALOMİD'İN MOLEKÜLER YAPISI VE TİTREŞİM FREKANSLARI Özet: Temel haldeki N-aminofitalamidin (NAPH moleküler yapısı, titreşim frekansları ve uygun mod tanımlamaları, 6-31 G (d, p temel setli Hartree-Fock (HF ve yoğunluk fonksiyonu metodları (B3LYP kullanılarak hesaplandı. Hesaplamalar, NAPH'ın CS simetrisine uyarlandı. Elde edilen titreşim frekansları ve optimize geometrik parametreleri (bağ uzunlukları ve bağ açıları, deneysel değerlerle iyi bir uyum içinde olduğu görüldü. Deneysel ve teorik sonuçların karşılaştırılması, B3LYP'nin HF metodundan daha üstün olduğunu gösterdi. Ayrıca teorik infrared şiddetleri ve Raman aktiviteleri verildi. Anahtar Kelimeler: N-aminofitalamidin; titreşimler; IR spektrumu; Raman Spektrumu; HF; DFT

  20. Hydrogen and dihydrogen bonding of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  1. Electronic response of rare-earth magnetic-refrigeration compounds GdX2 (X = Fe and Co)

    Science.gov (United States)

    Bhatt, Samir; Ahuja, Ushma; Kumar, Kishor; Heda, N. L.

    2018-05-01

    We present the Compton profiles (CPs) of rare-earth-transition metal compounds GdX2 (X = Fe and Co) using 740 GBq 137Cs Compton spectrometer. To compare the experimental momentum densities, we have also computed the CPs, electronic band structure, density of states (DOS) and Mulliken population (MP) using linear combination of atomic orbitals (LCAO) method. Local density and generalized gradient approximations within density functional theory (DFT) along with the hybridization of Hartree-Fock and DFT (B3LYP and PBE0) have been considered under the framework of LCAO scheme. It is seen that the LCAO-B3LYP based momentum densities give a better agreement with the experimental data for both the compounds. The energy bands and DOS for both the spin-up and spin-down states show metallic like character of the reported intermetallic compounds. The localization of 3d electrons of Co and Fe has also been discussed in terms of equally normalized CPs and MP data. Discussion on magnetization using LCAO method is also included.

  2. CrystalExplorer model energies and energy frameworks: extension to metal coordination compounds, organic salts, solvates and open-shell systems

    Directory of Open Access Journals (Sweden)

    Campbell F. Mackenzie

    2017-09-01

    Full Text Available The application domain of accurate and efficient CE-B3LYP and CE-HF model energies for intermolecular interactions in molecular crystals is extended by calibration against density functional results for 1794 molecule/ion pairs extracted from 171 crystal structures. The mean absolute deviation of CE-B3LYP model energies from DFT values is a modest 2.4 kJ mol−1 for pairwise energies that span a range of 3.75 MJ mol−1. The new sets of scale factors determined by fitting to counterpoise-corrected DFT calculations result in minimal changes from previous energy values. Coupled with the use of separate polarizabilities for interactions involving monatomic ions, these model energies can now be applied with confidence to a vast number of molecular crystals. Energy frameworks have been enhanced to represent the destabilizing interactions that are important for molecules with large dipole moments and organic salts. Applications to a variety of molecular crystals are presented in detail to highlight the utility and promise of these tools.

  3. Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

    Science.gov (United States)

    Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

    2012-10-30

    The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. DFT approach to (benzylthio)acetic acid: Conformational search, molecular (monomer and dimer) structure, vibrational spectroscopy and some electronic properties

    Science.gov (United States)

    Sienkiewicz-Gromiuk, Justyna

    2018-01-01

    The DFT studies were carried out with the B3LYP method utilizing the 6-31G and 6-311++G(d,p) basis sets depending on whether the aim of calculations was to gain the geometry at equilibrium, or to calculate the optimized molecular structure of (benzylthio)acetic acid (Hbta) in the forms of monomer and dimer. The minimum conformational energy search was followed by the potential energy surface (PES) scan of all rotary bonds existing in the acid molecule. The optimized geometrical monomeric and dimeric structures of the title compound were compared with the experimental structural data in the solid state. The detailed vibrational interpretation of experimental infrared and Raman bands was performed on the basis of theoretically simulated ESFF-scaled wavenumbers calculated for the monomer and dimer structures of Hbta. The electronic characteristics of Hbta is also presented in terms of Mulliken atomic charges, frontier molecular orbitals and global reactivity descriptors. Additionally, the MEP and ESP surfaces were computed to predict coordination sites for potential metal complex formation.

  5. 3-Ishwarone, a Rare Ishwarane Sesquiterpene from Peperomia scandens Ruiz & Pavon: Structural Elucidation through a Joint Experimental and Theoretical Study

    Directory of Open Access Journals (Sweden)

    Fernando M. dos S.

    2013-10-01

    Full Text Available 3-Ishwarone, (1, a sesquiterpene with a rare ishwarane skeleton, was isolated from Peperomia scandens Ruiz & Pavon (Piperaceae. Its structure was unambiguously determined by 1D- and 2D-NMR and infrared analyses, as well as by comparative theoretical studies which involved calculations of 13C-NMR chemical shifts, using the Density Functional Theory (DFT with the mPW1PW91 hybrid functional and Pople’s 6-31G(d basis set, and of vibrational frequencies, using the B3LYP hybrid functional and triple ζ Dunning’s correlation consistent basis set (cc-pVTZ, of (1 and three of its possible diastereomers, compounds 2–4.

  6. Study on structure, vibrational analysis and molecular characteristics of some halogen substituted azido-phenylethanones using FTIR spectra and DFT

    Science.gov (United States)

    Prashanth, J.; Reddy, Byru Venkatram

    2018-03-01

    The Fourier transform infrared (FTIR) spectra of organic compounds 4-fluoro-2-azido-1-phenylethanone (FAP), 4-chloro-2-azido-1-phenylethanone (CAP) and 4-bromo-2-azido-1-phenylethanone (BAP) have been recorded in the region 4000-400 cm-1. The optimized molecular structure for global minimum energy of the titled molecules is determined by evaluating torsional potentials as a function of rotation angle about free rotation bonds among the substituent groups subjecting them to DFT employing B3LYP functional with 6-311++G (d,p) basis set. The vibrational frequencies along with infrared intensities are computed by SQM procedure. The rms error between observed and calculated frequencies is found to be 9.27, 8.17 and 7.95 cm-1 for FAP, CAP and BAP, respectively which shows good agreement between experimental and scaled values of calculated frequencies obtained by DFT. The vibrational assignments of all the fundamental bands of each molecule are made unambiguously using PED and eigen vectors obtained in the computations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the titled molecules exhibit NLO behaviour and hence may be considered for potential applicants for the development of NLO materials. HOMO and LUMO energies evaluated in the study demonstrate chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyper conjugative interactions and charge delocalization. The molecular electrostatic surface potential (MESP) and thermodynamic parameters are also evaluated.

  7. Characterizing the potential energy surface of the water dimer with DFT: failures of some popular functionals for hydrogen bonding.

    Science.gov (United States)

    Anderson, Julie A; Tschumper, Gregory S

    2006-06-08

    Ten stationary points on the water dimer potential energy surface have been examined with ten density functional methods (X3LYP, B3LYP, B971, B98, MPWLYP, PBE1PBE, PBE, MPW1K, B3P86, and BHandHLYP). Geometry optimizations and vibrational frequency calculations were carried out with the TZ2P(f,d)+dif basis set. All ten of the density functionals correctly describe the relative energies of the ten stationary points. However, correctly describing the curvature of the potential energy surface is far more difficult. Only one functional (BHandHLYP) reproduces the number of imaginary frequencies from CCSD(T) calculations. The other nine density functionals fail to correctly characterize the nature of at least one of the ten (H(2)O)(2) stationary points studied here.

  8. Theoretical Study on Vibrational Spectra, Detonation Properties and Pyrolysis Mechanism for Cyclic 2-Diazo-4,6-dinitrophenol

    Science.gov (United States)

    Li, Xiao-hong; Yin, Geng-xin; Zhang, Xian-zhou

    2012-10-01

    Based on the full optimized molecular geometrical structures at the DFT-B3LYP/6-311+G** level, there exists intramolecular hydrogen bond interaction for cyclic 2-diazo-4,6-dinitrophenol. The assigned infrared spectrum is obtained and used to compute the thermodynamic properties. The results show that there are four main characteristic regions in the calculated IR spectra of the title compound. The detonation velocities and pressures are also evaluated by using Kamlet-Jacobs equations based on the calculated density and condensed phase heat of formation. Thermal stability and the pyrolysis mechanism of 2-diazo-4,6-dinitrophenol are investigated by calculating the bond dissociation energies at the B3LYP/6-311+G** level.

  9. Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

    Science.gov (United States)

    Sagdinc, Seda; Pir, Hacer

    2009-07-01

    The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.

  10. 3,3'-[(E-eten-1,2-diil]di(9-heksil-9H-karbazol bileşiğinin sentezi, X-ışını yapı tayini ve teorik yapı tahmini

    Directory of Open Access Journals (Sweden)

    Erol Asker

    2016-08-01

    Full Text Available 3,3'-[(E-eten-1,2-diil]di(9-heksil-9H-karbazol bileşiği 9H-karbazoldan çıkarak üç basamakta sentezlenmiş ve yapısı spektroskopik yöntemlerle aydınlatılmıştır. Kristal yapısı monoklinik uzay grubu P21/c'de çözülmüş ve geometrik özellikleri yarı-deneysel PM7 ve teorik DFT/B3LYP hesaplamalarla elde edilen verilerle karşılaştırılmıştır. DFT hesapsal sonuçlar ile X-ışını kırınımı deneysel sonuçlar arasında yüksek korelasyon belirlenmiştir. Kristal yapıdaki moleküller arası etkileşimler hesaplanan öncü orbitallerle açıklanmaya çalışılmıştır.

  11. Effect of aromatization of the ring on intramolecular H-bond in 3-hydroxy-4-formylo derivatives of fulvene

    Science.gov (United States)

    Oziminski, Wojciech P.; Krygowski, Tadeusz M.

    2011-06-01

    DFT optimization of H-bonded 3-hydroxy-4-formylo derivatives of fulvene aromatized by amino substitution at C6 or by complexation with Li atom was performed using the B3LYP functional together with 6-311+G(d,p) basis set. Several aromaticity indicators (HOMA, NICS, pEDA and Shannon aromaticity) confirm an increase of aromaticity in the sequence: fulvene, 6-aminofulvene, Li-complex with fulvene and in the case of H-bonded 3-hydroxy-4-formylo derivatives, exhibited in the same sequence an increase of H-bond strength estimated by direct comparison of energy for H-bonded and open conformations, as well as by using AIM based electron densities at bond critical point.

  12. Supramolecular architecture of 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole.3H2O: Synthesis, spectroscopic investigations, DFT computation, MD simulations and docking studies

    Science.gov (United States)

    Murthy, P. Krishna; Smitha, M.; Sheena Mary, Y.; Armaković, Stevan; Armaković, Sanja J.; Rao, R. Sreenivasa; Suchetan, P. A.; Giri, L.; Pavithran, Rani; Van Alsenoy, C.

    2017-12-01

    Crystal and molecular structure of newly synthesized compound 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole (BMMBI) has been authenticated by single crystal X-ray diffraction, FT-IR, FT-Raman, 1H NMR, 13C NMR and UV-Visible spectroscopic techniques; compile both experimental and theoretical results which are performed by DFT/B3LYP/6-311++G(d,p) method at ground state in gas phase. Visualize nature and type of intermolecular interactions and crucial role of these interactions in supra-molecular architecture has been investigated by use of a set of graphical tools 3D-Hirshfeld surfaces and 2D-fingerprint plots analysis. The title compound stabilized by strong intermolecular hydrogen bonds N⋯Hsbnd O and O⋯Hsbnd O, which are envisaged by dark red spots on dnorm mapped surfaces and weak Br⋯Br contacts envisaged by red spot on dnorm mapped surface. The detailed fundamental vibrational assignments of wavenumbers were aid by with help of Potential Energy distribution (PED) analysis by using GAR2PED program and shows good agreement with experimental values. Besides frontier orbitals analysis, global reactivity descriptors, natural bond orbitals and Mullikan charges analysis were performed by same basic set at ground state in gas phase. Potential reactive sites of the title compound have been identified by ALIE, Fukui functions and MEP, which are mapped to the electron density surfaces. Stability of BMMBI have been investigated from autoxidation process and pronounced interaction with water (hydrolysis) by using bond dissociation energies (BDE) and radial distribution functions (RDF), respectively after MD simulations. In order to identify molecule's most important reactive spots we have used a combination of DFT calculations and MD simulations. Reactivity study encompassed calculations of a set of quantities such as: HOMO-LUMO gap, MEP and ALIE surfaces, Fukui functions, bond dissociation energies and radial distribution functions. To confirm the potential

  13. One Pot Selective Arylation of 2-Bromo-5-Chloro Thiophene; Molecular Structure Investigation via Density Functional Theory (DFT), X-ray Analysis, and Their Biological Activities.

    Science.gov (United States)

    Rasool, Nasir; Kanwal, Aqsa; Rasheed, Tehmina; Ain, Quratulain; Mahmood, Tariq; Ayub, Khurshid; Zubair, Muhammad; Khan, Khalid Mohammed; Arshad, Muhammad Nadeem; M Asiri, Abdullah; Zia-Ul-Haq, Muhammad; Jaafar, Hawa Z E

    2016-06-28

    Synthesis of 2,5-bisarylthiophenes was accomplished by sequential Suzuki cross coupling reaction of 2-bromo-5-chloro thiophenes. Density functional theory (DFT) studies were carried out at the B3LYP/6-31G(d, p) level of theory to compare the geometric parameters of 2,5-bisarylthiophenes with those from X-ray diffraction results. The synthesized compounds are screened for in vitro bacteria scavenging abilities. At the concentration of 50 and 100 μg/mL, compounds 2b, 2c, 2d, 3c, and 3f with IC50-values of 51.4, 52.10, 58.0, 56.2, and 56.5 μg/mL respectively, were found most potent against E. coli. Among all the synthesized compounds 2a, 2d, 3c, and 3e with the least values of IC50 77, 76.26, 79.13 μg/mL respectively showed significant antioxidant activities. Almost all of the compounds showed good antibacterial activity against Escherichia coli, whereas 2-chloro-5-(4-methoxyphenyl) thiophene (2b) was found most active among all synthesized compound with an IC50 value of 51.4 μg/mL. All of the synthesized compounds were screened for nitric oxide scavenging activity as well. Frontier molecular orbitals (FMOs) and molecular electrostatic potentials of the target compounds were also studied theoretically to account for their relative reactivity.

  14. 64Cu-Labeled LyP-1-Dendrimer for PET-CT Imaging of Atherosclerotic Plaque

    Science.gov (United States)

    2015-01-01

    The ability to detect and quantify macrophage accumulation can provide important diagnostic and prognostic information for atherosclerotic plaque. We have previously shown that LyP-1, a cyclic 9-amino acid peptide, binds to p32 proteins on activated macrophages, facilitating the visualization of atherosclerotic plaque with PET. Yet, the in vivo plaque accumulation of monomeric [18F]FBA-LyP-1 was low (0.31 ± 0.05%ID/g). To increase the avidity of LyP-1 constructs to p32, we synthesized a dendritic form of LyP-1 on solid phase using lysine as the core structural element. Imaging probes (FAM or 6-BAT) were conjugated to a lysine or cysteine on the dendrimer for optical and PET studies. The N-terminus of the dendrimer was further modified with an aminooxy group in order to conjugate LyP-1 and ARAL peptides bearing a ketone. Oxime ligation of peptides to both dendrimers resulted in (LyP-1)4- and (ARAL)4-dendrimers with optical (FAM) and PET probes (6-BAT). For PET-CT studies, (LyP-1)4- and (ARAL)4-dendrimer-6-BAT were labeled with 64Cu (t1/2 = 12.7 h) and intravenously injected into the atherosclerotic (ApoE–/–) mice. After two hours of circulation, PET-CT coregistered images demonstrated greater uptake of the (LyP-1)4-dendrimer-64Cu than the (ARAL)4-dendrimer-64Cu in the aortic root and descending aorta. Ex vivo images and the biodistribution acquired at three hours after injection also demonstrated a significantly higher uptake of the (LyP-1)4-dendrimer-64Cu (1.1 ± 0.26%ID/g) than the (ARAL)4-dendrimer-64Cu (0.22 ± 0.05%ID/g) in the aorta. Similarly, subcutaneous injection of the LyP-1-dendrimeric carriers resulted in preferential accumulation in plaque-containing regions over 24 h. In the same model system, ex vivo fluorescence images within aortic plaque depict an increased accumulation and penetration of the (LyP-1)4-dendrimer-FAM as compared to the (ARAL)4-dendrimer-FAM. Taken together, the results suggest that the (LyP-1)4-dendrimer can be applied for in

  15. Quantum-chemical study on the bioactive conformation of epothilones.

    Science.gov (United States)

    Jiménez, Verónica A

    2010-12-27

    Herein, I report a DFT study on the bioactive conformation of epothilone A based on the analysis of 92 stable conformations of free and bound epothilone to a reduced model of tubulin receptor. The equilibrium structures and relative energies were studied using B3LYP and X3LYP functionals and the 6-31G(d) standard basis set, which was considered appropriate for the size of the systems under study. Calculated relative energies of free and bound epothilones led me to propose a new model for the bioactive conformation of epothilone A, which accounts for several structure-activity data.

  16. The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties

    OpenAIRE

    Xu, Xin; Goddard, William A., III

    2004-01-01

    We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energ...

  17. Crystal structure, solvothermal synthesis, thermogravimetric studies and DFT calculations of a five-coordinate cobalt(II) compound based on the N,N-bis-(2-hy-droxy-eth-yl)glycine anion.

    Science.gov (United States)

    Zhou, Yanling; Liu, Xianrong; Wang, Qijun; Wang, Lisheng; Song, Baoling

    2016-10-01

    The reaction of CoCl 2 ·6H 2 O, N , N -bis-(2-hy-droxy-eth-yl)glycine and tri-ethyl-amine (Et 3 N) in ethanol solution under solvothermal conditions produced crystals of [ N , N -bis-(2-hy-droxy-eth-yl)glycinato]chloridocobalt(II), [Co(C 6 H 12 NO 4 )Cl]. The Co II ion is coordinated in a slightly distorted trigonal-bipyramidal environment which is defined by three O atoms occupying the equatorial plane and the N and Cl atoms in the apical sites. In the crystal, two types of O-H⋯O hydrogen bonds connect the mol-ecules, forming a two-dimensional network parallel to (001). The mol-ecular structure of the title compound confirms the findings of FTIR, elemental analysis, ESI-MS analysis and TG analysis. By using the density functional theory (DFT) (B3LYP) method with 6-31G(d) basis set, the molecular structure has been calculated and optimized.

  18. Theoretical description of copper Cu(I)/Cu(II) complexes in mixed ammine-aqua environment. DFT and ab initio quantum chemical study

    International Nuclear Information System (INIS)

    Pavelka, Matej; Burda, Jaroslav V.

    2005-01-01

    This work is devoted to investigate the interactions of the Cu(I)/Cu(II) cation with variable ammonia-water ligand field by the quantum chemical approach. For that purpose, the optimization of the [Cu(NH 3 ) m (H 2 O) n ] 2+/+ complexes (where n varies from 0 to 4 or 6 and m + n = 4 or 6) has been performed at the DFT/6-31+G(d) level of theory in conjunction with the B3PW91 hybrid functional. Based on the results of the single-point B3LYP/6-311++G(2df,2pd) calculations, the stabilization energies were determined. The two-coordinated copper(I) complexes appeared to be the most stable compounds with the remaining water or ammonia molecules in the second solvation shell. In the case of the Cu(II) systems, four-coordinated complexes were found to be the most stable. In order to examine and explain bonding characteristics, Morokuma interaction energy decomposition (for selected Cu + complexes) and Natural Population Analysis for all systems were performed. It was found that the most stable structures correlate with the highest donation effects. Therefore, more polarizable ammonia molecules exhibit higher donation than water and thus make stronger bonds to copper. This can be demonstrated by the fact that the NH 3 molecule always tries to occupy the first solvation shell in mixed ammine-aqua complexes

  19. Combine experimental and theoretical investigation on an alkaloid-Dimethylisoborreverine

    Science.gov (United States)

    Singh, Swapnil; Singh, Harshita; Karthick, T.; Agarwal, Parag; Erande, Rohan D.; Dethe, Dattatraya H.; Tandon, Poonam

    2016-01-01

    A combined experimental (FT-IR, 1H and 13C NMR) and theoretical approach is used to study the structure and properties of antimalarial drug dimethylisoborreverine (DMIB). Conformational analysis, has been performed by plotting one dimensional potential energy curve that was computed using density functional theory (DFT) with B3LYP/6-31G method and predicted conformer A1 as the most stable conformer. After full geometry optimization, harmonic wavenumbers were computed for conformer A1 at the DFT/B3LYP/6-311++G(d,P) level. A complete vibrational assignment of all the vibrational modes have been performed on the bases of the potential energy distribution (PED) and theoretical results were found to be in good agreement with the observed data. To predict the solvent effect, the UV-Vis spectra were calculated in different solvents by polarizable continuum model using TD-DFT method. Molecular docking studies were performed to test the biological activity of the sample using SWISSDOCK web server and Hex 8.0.0 software. The molecular electrostatic potential (MESP) was plotted to identify the reactive sites of the molecule. Natural bond orbital (NBO) analysis was performed to get a deep insight of intramolecular charge transfer. Thermodynamical parameters were calculated to predict the direction of chemical reaction.

  20. Analysis of molecular structure and vibrational spectra of hexadecyl (cetyl) trimethylammonium brode (CTAB)

    International Nuclear Information System (INIS)

    Goekce, H.; Bahceli, S.

    2010-01-01

    FT-IR and Raman spectra of CTAB [C 1 6H 3 3N(CH 3 ) 3 ] + Br - have been experimentally recorded in the region 550-4000 cm - 1 and 400-3100 cm - 1, respectively. The molecular geometry and vibrational frequencies of CTAB in the ground state have been calculated by using ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with the 6-31+G(d,p) basis set. The obtained optimized geometric parameters (bond lengths and bond angles) and vibrational frequencies were in very good agreement with the experimental data. The comparisons of the observed fundamental vibrational frequencies and calculated results for the fundamental vibrational frequencies of CTAB shows that the scaled B3LYP method is superior compared to the scaled HF method.

  1. Energy and spectrum of BeO molecule under the electric field from different directions

    NARCIS (Netherlands)

    Jiang, M.; Guo, F. J.; Yan, A. Y.; Zhang, C. W.; Miao, F.

    2010-01-01

    Based on the density functional theory DFT/ B3LYP at 6-311g level, the ground states of BeO molecule are optimized. The effects of electric field on the bond length, the system energy, the charge distribution, the energy levels, the HOMO-LUMO gaps and the infrared spectrum of BeO molecule are

  2. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Its molecular geometry in the ground state has also been calculated using density functional theory (DFT) at the B3LYP/6-31G∗∗ level and compared with its crystal structure. Results show that the optimized geometry can well reproduce the crystal structure. Furthermore, both absorption and emission spectra of 1 and 2 ...

  3. Atmospheric Oxidation Mechanism and Kinetic Studies for OH and NO3 Radical-Initiated Reaction of Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Rui Gao

    2014-03-01

    Full Text Available The mechanism for OH and NO3 radical-initiated oxidation reactions of methyl methacrylate (MMA was investigated by using density functional theory (DFT molecular orbital theory. Geometrical parameters of the reactants, intermediates, transition states, and products were fully optimized at the B3LYP/6-31G(d,p level. Detailed oxidation pathways were presented and discussed. The rate constants were deduced by the canonical variational transition-state (CVT theory with the small-curvature tunneling (SCT correction and the multichannel Rice-Ramspergere-Kassele-Marcus (RRKM theory, based on the potential energy surface profiles over the general atmospheric temperature range of 180–370 K. The calculated results were in reasonable agreement with experimental measurement.

  4. In search for an optimal methodology to calculate the valence electron affinities of temporary anions.

    Science.gov (United States)

    Puiatti, Marcelo; Vera, D Mariano A; Pierini, Adriana B

    2009-10-28

    Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.

  5. Breathing Raman modes in Ag{sub 2}S nanoparticles obtained from F9 zeolite matrix

    Energy Technology Data Exchange (ETDEWEB)

    Delgado-Beleño, Y. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Cortez-Valadez, M., E-mail: jose.cortez@unison.mx [CONACYT Research Fellow, Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico); Martinez-Nuñez, C.E.; Britto Hurtado, R.; Alvarez, Ramón A.B.; Rocha-Rocha, O.; Arizpe-Chávez, H.; Perez-Rodríguez, A.; Flores-Acosta, M. [Departamento de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Son. (Mexico)

    2015-12-16

    Highlights: • Raman breathing modes in small silver sulfide nanoparticles. • Low energy (AgS){sub n} clusters. • Vibrational spectra predicted by DFT. • Zeolite synthesis for small nanoparticles. - Abstract: Ag{sub 2}S nanoparticles were synthesized with a combination of synthetic F9, silver nitrate (AgNO{sub 3}) and monohydrated sodium sulfide (Na{sub 2}S{sub 9}H{sub 2}O). An ionic exchange was achieved via hydrothermal reaction. Nanoparticles with a predominant size ranging from 2 to 3 nm were obtained through Transmission Electron Microscopy (TEM). The nanoparticles feature a phase P21/n (14) monoclinic structure. A Raman band can be observed at around 250 cm{sup −1} in the nanoparticles. Furthermore, the vibrational properties and stability parameters of the clusters (AgS){sub n}, (with n = 2–9) were studied by the Density Functional Theory (DFT). The approximation levels used with DFT were: Local Spin Density Approximation (LSDA) and Becke’s three-parameter and the gradient corrected functional of Lee, Yang and Puar (B3LYP) in combination with the basis set LANL2DZ (the effective core potentials and associated double-zeta valence). The Radial Breathing Mode (RBM) for B3LYP was found between 227 and 295 cm{sup −1} as well as in longer wavelengths for LSDA.

  6. Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Norrby, Per-Ola

    2007-01-01

    Oxidative addition of aryl chlorides to palladium has been investigated by hybrid density functional theory methods (B3LYP), including a continuum model describing the solvent implicitly. A series of para-substituted aryl chlorides were studied to see the influence of electronic effects...

  7. Conformational, structural, vibrational, electronic and quantum chemical investigations of cis-2-methoxycinnamic acid

    Science.gov (United States)

    Arjunan, V.; Anitha, R.; Marchewka, M. K.; Mohan, S.; Yang, Haifeng

    2015-01-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of cis-2-methoxycinnamic acid have been measured in the range 4000-400 and 4000-100 cm-1, respectively. Complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the observed FTIR and FT-Raman data. The geometry was optimised without any symmetry constrains using the DFT/B3LYP method utilising 6-311++G∗∗ and cc-pVTZ basis sets. The thermodynamic stability and chemical reactivity descriptors of the molecule have been determined. The exact environment of C and H of the molecule has been analysed by NMR spectroscopies through 1H and 13C NMR chemical shifts of the molecule. The energies of the frontier molecular orbitals have also been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. The vibrational frequencies which were determined experimentally are compared with those obtained theoretically from density functional theory (DFT) gradient calculations employing the B3LYP/6-311++G∗∗ and cc-pVTZ methods.

  8. Using non-empirically tuned range-separated functionals with simulated emission bands to model fluorescence lifetimes.

    Science.gov (United States)

    Wong, Z C; Fan, W Y; Chwee, T S; Sullivan, Michael B

    2017-08-09

    Fluorescence lifetimes were evaluated using TD-DFT under different approximations for the emitting molecule and various exchange-correlation functionals, such as B3LYP, BMK, CAM-B3LYP, LC-BLYP, M06, M06-2X, M11, PBE0, ωB97, ωB97X, LC-BLYP*, and ωB97X* where the range-separation parameters in the last two functionals were tuned in a non-empirical fashion. Changes in the optimised molecular geometries between the ground and electronically excited states were found to affect the quality of the calculated lifetimes significantly, while the inclusion of vibronic features led to further improvements over the assumption of a vertical electronic transition. The LC-BLYP* functional was found to return the most accurate fluorescence lifetimes with unsigned errors that are mostly within 1.5 ns of experimental values.

  9. Synthesis, spectroscopic studies, DFT calculations, electrochemical evaluation, BSA binding and molecular docking of an aroylhydrazone -based cis-dioxido Mo(VI) complex

    Science.gov (United States)

    Mohamadi, Maryam; Faghih-Mirzaei, Ehsan; Ebrahimipour, S. Yousef; Sheikhshoaie, Iran; Haase, Wolfgang; Foro, Sabine

    2017-07-01

    A cis-dioxido Mo(VI) complex, [MoO2(L)(MeOH)], [L2-: (3-methoxy-2-oxidobenzylidene) benzohydrazonate], has been synthesized and characterized using physicochemical and spectroscopic techniques including elemental analysis, FT-IR, 1HNMR, UV-Vis spectroscopy, molar conductivity and single crystal X-ray diffraction. DFT calculations in the ground state of the complex were carried out using hybrid functional B3LYP with DGDZVP as basis set. Non-linear optical properties including electric dipole moment (μ), polarizability (α) and molecular first hyperpolarizability (β) of the compound were also computed. The values of linear polarizability and first hyperpolarizability obtained for the studied molecule indicated that the compound could be a good candidate of nonlinear optical materials. TD-DFT calculation and molecular electrostatic potential (MEP) were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the complex at different temperatures have been calculated. The interaction of a synthesized complex, with bovine serum albumin was also thoroughly investigated using experimental and theoretical studies. UV-Vis absorption and fluorescence quenching techniques were used to determine the binding parameters as well as the mechanism of the interaction. The values of binding constants were in the range of 104-105 M-1 demonstrating a moderate interaction between the synthesized complex and BSA making the protein suitable for transportation and delivery of the compound. Thermodynamic parameters were also indicating a binding through van der Waals force or hydrogen bond of [MoO2(L)(MeOH)] to BSA. The results obtained from docking studies were consistent to those obtained from experimental studies.

  10. Synthesis, crystal structure of and DFT calculations on bisglycinato-bis[p-(hydroxymethylpyridine]nickel(II

    Directory of Open Access Journals (Sweden)

    FANG FANG JIAN

    2010-09-01

    Full Text Available The main aim of this study was to investigate the relationship between mIn tA new Ni(II complex of bisglycinato-bis[p-(hydroxylmethylpy-ridine] was synthesized and characterized by elemental analysis, IR, UV–Vis spectroscopy and X-ray single crystal diffraction analysis. The thermal stability of the title complex was also determined. The complex adopts a distorted octahedral geometry and possesses inversion symmetry with the Ni(II ion as the center of inversion. Density function theory (DFT calculations of the structure, electronic absorption spectra, electron structure and natural population analysis (NPA at the B3LYP/LANL2DZ level of theory were performed. The predicted geometric parameters and electronic spectra were compared with the experimental values and they supported each other. The NPA results indicate that the electronic transitions were mainly derived from the contribution of an intra-ligand (IL transition, a ligand-to-metal charge transfer (LMCT transition and a d-d transition. The electron structure calculations suggest that the central Ni(II ion uses its 4s and 3d orbitals to form covalent bonds with coordinated N and O atoms. The calculated bond orders are also consistent with the thermal decomposition results. Based on vibrational analysis, the thermodynamic properties of the title complex were predicted and the correlative equations between these thermodynamic properties and temperature are also reported.

  11. A theoretical study on 3-(4-methoxyphenyl)-1-(pyridin-2-Yl) prop-2-en-1-one

    Energy Technology Data Exchange (ETDEWEB)

    Öner, Nazmiye, E-mail: fizikcinaz@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Avci, Davut, E-mail: davcir@sakarya.edu.tr; Atalay, Yusuf, E-mail: yatalay@sakarya.edu.tr [Sakarya University, Faculty of Arts and Sciences, Department of Physics, 54187, Sakarya (Turkey)

    2016-03-25

    This study reports the geometric parameters, vibration frequencies, {sup 13}C and {sup 1}H NMR chemical shifts of 3-(4-Methoxyphenyl)-1-(pyridin-2-yl) prop-2-en-1-one (MPP) molecule calculated by B3LYP level of density functional theory (DFT) with 6-311++G(d,p) basis set. {sup 13}C and {sup 1}H NMR chemical shifts were calculated within GIAO approach which is one of the most common approaches. Additionally, 3D molecular surfaces such as molecular electrostatic potential (MEP) and electrostatic potential (ESP), were simulated by the same level. As a result, obtained theoretical results were found to be consistent with experimental ones. All of calculations were carried out Gaussian 09 package program.

  12. Syntheses, spectroscopic properties and molecular structure of silver phytate complexes - IR, UV-VIS studies and DFT calculations

    Science.gov (United States)

    Zając, A.; Dymińska, L.; Lorenc, J.; Ptak, M.; Hanuza, J.

    2018-03-01

    Silver phytate IP6, IP6Ag, IP6Ag2 and IP6Ag3 complexes in the solid state have been synthesized changing the phosphate to metal mole ratio. The obtained products have been characterized by means of chemical and spectroscopic studies. Attenuated total reflection Fourier transform infrared technique and Raman microscope were used in the measurements. These results were discussed in terms of DFT (Density Functional Theory) quantum chemical calculations using the B3LYP/6-31G(d,p) approach. The molecular structures of these compounds have been proposed on the basis of group theory and geometry optimization taking into account the shape and the number of the observed bands corresponding to the stretching and bending vibrations of the phosphate group and metal-oxygen polyhedron. The role of inter- and intra-hydrogen bonds in stabilization of the structure has been discussed. It was found that three types of hydrogen bonds appear in the studied compounds: terminal, and those engaged in the inter- and intra-molecular interactions. The Fermi resonance as a result of the strong intra-molecular Osbnd H⋯O hydrogen bonds was discovered. Electron absorption spectra have been measured to characterize the electron properties of the studied complexes and their local symmetry.

  13. Enhancement in (BHmax of PLD-made isotropic Nd-Fe-B thick film magnets deposited on Si substrates

    Directory of Open Access Journals (Sweden)

    M. Nakano

    2017-05-01

    Full Text Available Increase in Nd contents of a PLD-made isotropic Nd-Fe-B thick-film magnet enabled us to enhance the thickness of the film magnet deposited on a Si substrate because the linear expansion coefficient of Nd is an intermediate value between Nd2Fe14B and Si. The large amount of Nd, however, degraded the residual magnetic polarization and (BHmax. In the study, we reduced the Nd contents of each Nd-Fe-B film by inserting a Nd or a Nd-rich Nd-Fe-B buffer layer between a Nd-Fe-B film and a Si substrate in order to suppress the mechanical destruction together with the improvement in magnetic properties. It was found that the mechanical property of a Nd-Fe-B film comprising the Nd-Fe-B buffer layer in the thickness range from 10 to 60 μm was superior than that of a sample with the Nd buffer layer. Resultantly, an average (BHmax value of Nd-Fe-B films with each Nd-Fe-B buffer layer deposited on Si substrates could be enhanced by approximately 15 kJ/m3 compared to that of non-buffer-layered films.

  14. Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C-60 to Afford Efficient Photodriven Charge Separation

    DEFF Research Database (Denmark)

    Supur, M.; Kawashima, Y.; Larsen, K. R.

    2014-01-01

    ) obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6-311G(d,p) level, the orbital interactions between the crown ether moieties and the p surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation...

  15. Research Article

    African Journals Online (AJOL)

    2017-01-01

    Jan 1, 2017 ... In this study, fourteen tautomers have been subjected to two types of calculation: DFT/B3LYP and MP2. 1.2 Computational details. All calculations at this work were performed on a personal computer by means of. GAUSSIAN 09 program package [5]. The second-order Moller–Plesset (MP2) and density ...

  16. Solvent effect in implicit/explicit model on FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra, linear, second- and third-nonlinear optical parameters of 2-(trifluoromethyl)benzoic acid: Experimental and computational study

    Science.gov (United States)

    Avcı, Davut; Altürk, Sümeyye; Tamer, Ömer; Kuşbazoğlu, Mustafa; Atalay, Yusuf

    2017-09-01

    FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra for 2-(trifluoromethyl)benzoic acid (2-TFMBA) were recorded. DFT//B3LYP/6-31++G(d,p) calculations were used to determine the optimized molecular geometry, vibrational frequencies, 1H, 13C and 19F GIAO-NMR chemical shifts of 2-TFMBA. The detailed assignments of vibrational frequencies were carried out on the basis of potential energy distribution (PED) by using VEDA program. TD-DFT/B3LYP/6-31++G(d,p) calculations with the PCM (polarizable continuum model) in ethanol and DMSO solvents based on implicit/explicit model and gas phase in the excited state were employed to investigate UV-vis absorption and fluorescence emission wavelengths. The UV-vis and emission spectra were given in ethanol and DMSO solvents, and the major contributions to the electronic transitions were obtained. In addition, the NLO parameters (β, γ and χ(3)) and frontier molecular orbital energies of 2-TFMBA were calculated by using B3LYP/6-31++G(d,p) level. The NLO parameters of 2-TFMBA were compared with that of para-Nitroaniline (pNA) and urea which are the typical NLO materials. The refractive index (n) is calculated by using the Lorentz-Lorenz equation to observe polarization behavior of 2-TFMBA in DMSO and ethanol solvents. In order to investigate intramolecular and hydrogen bonding interactions, NBO calculations were also performed by the same level. To sum up, considering the well-known biological role, photochemical properties of 2-TFMBA were discussed.

  17. Molecular structure, spectral studies, NBO, HOMO-LUMO profile, MEP and Mulliken analysis of 3β,6β-dichloro-5α-hydroxy-5α-cholestane

    Science.gov (United States)

    Alam, Mahboob; Park, Soonheum

    2018-05-01

    The synthesis of 3β,6β-dichloro-5α-hydroxy-5α-cholestane (in general, steroidal chlorohydrin or steroidal halohydrin) and theoretical study of the structure are reported in this paper. The individuality of chlorohydrin was confirmed by FT-IR, NMR, MS, CHN microanalysis and X-ray crystallography. DFT calculations on the titled molecule have been performed. The molecular structure and spectra explained by Gaussian hybrid computational analysis theory (B3LYP) are found to be in correlation with the experimental data obtained from the various spectrophotometric techniques. The theoretical geometry optimization data were compared with the X-ray data. The vibrational bands appearing in the FT-IR are assigned with accuracy using harmonic frequencies along with intensities and animated modes. Molecular properties like NBO, HOMO-LUMO analysis, chemical reactivity descriptors, MEP mapping and dipole moment have been dealt at same level of theory. The calculated electronic spectrum of chlorohydrin is interpreted on the basis of TD-DFT calculations.

  18. Experimental and ab initio DFT calculated Raman Spectrum of Sudan I, a Red Dye

    DEFF Research Database (Denmark)

    Kunov-Kruse, Andreas Jonas; Kristensen, Steffen Buus; Liu, Chuan

    2011-01-01

    The red dye Sudan I was investigated by Raman spectroscopy using different excitation wavelengths (1064, 532 and 244 nm). A calculation of the Raman spectrum based on quantum mechanical ab initio density functional theory (DFT) was made using the RB3LYP method with the 3-21G and 6-311+G(d,p) basis...... of the Sudan I molecule was involved in the majority of the vibrations through N N and C–N stretching and various bending modes. Low-intensity bands in the lower wavenumber range (at about 721, 616, 463 and 218 cm−1) were selectively enhanced by the resonance Raman effect when using the 532 nm excitation line....... Comparison was made with other azo dyes in the literature on natural, abundant plant pigments. The results show that there is a possibility in foodstuff analysis to distinguish Sudan I from other dyes by using Raman spectroscopy with more than one laser wavelength for resonance enhancement of the different...

  19. Growth, structure, Hirshfeld surface and spectroscopic properties of 2-amino-4-hydroxy-6-methylpyrimidinium-2,3-pyrazinedicorboxylate single crystal

    Science.gov (United States)

    Faizan, Mohd; Alam, Mohammad Jane; Afroz, Ziya; Rodrigues, Vítor Hugo Nunes; Ahmad, Shabbir

    2018-03-01

    The present work is focused on the crystal structure, vibrational spectroscopy and DFT calculations of hydrogen bonded 2,3-pyrazinedicorboxylic acid and 2-amino-4-hydroxy-6-methylpyrimidine (PDCA-.AHMP+) crystal. The crystal structure has been determined using single crystal X-ray diffraction analysis which shows that the crystal belongs to monoclinic space group P21/n. The PDCA-.AHMP+ crystal has been characterized by FTIR, FT-Raman and FT-NMR spectroscopic techniques. The FTIR and FT-Raman spectra of the complex have unique spectroscopic feature as compared with those of the starting material to confirm salt formation. The theoretical vibrational studies have been performed to understand the modes of the vibrations of asymmetric unit of the complex by DFT methods. Hirschfeld surface and 2D fingerprint plots analyses were carried out to investigate the intermolecular interactions and its contribution in the building of PDCA-.AHMP+ crystal. The experimental and simulated 13C and 1H NMR studies have assisted in structural analysis of PDCA-.AHMP+ crystal. The electronic spectroscopic properties of the complex were explored by the experimental as well as theoretical electronic spectra simulated using TD-DFT/IEF-PCM method at B3LYP/6-311++G (d,p) level of theory. In addition, frontier molecular orbitals, molecular electrostatic potential map (MEP) and nonlinear optical (NLO) properties using DFT method have been also presented.

  20. NSAIDs as potential treatment option for preventing amyloid β toxicity in Alzheimer's disease: an investigation by docking, molecular dynamics, and DFT studies.

    Science.gov (United States)

    Azam, Faizul; Alabdullah, Nada Hussin; Ehmedat, Hadeel Mohammed; Abulifa, Abdullah Ramadan; Taban, Ismail; Upadhyayula, Sreedevi

    2018-06-01

    Aggregation of amyloid beta (Aβ) protein considered as one of contributors in development of Alzheimer's disease (AD). Several investigations have identified the importance of non-steroidal anti-inflammatory drugs (NSAIDs) as Aβ aggregation inhibitors. Here, we have examined the binding interactions of 24 NSAIDs belonging to eight different classes, with Aβ fibrils by exploiting docking and molecular dynamics studies. Minimum energy conformation of the docked NSAIDs were further optimized by density functional theory (DFT) employing Becke's three-parameter hybrid model, Lee-Yang-Parr (B3LYP) correlation functional method. DFT-based global reactivity descriptors, such as electron affinity, hardness, softness, chemical potential, electronegativity, and electrophilicity index were calculated to inspect the expediency of these descriptors for understanding the reactive nature and sites of the molecules. Few selected NSAID-Aβ fibrils complexes were subjected to molecular dynamics simulation to illustrate the stability of these complexes and the most prominent interactions during the simulated trajectory. All of the NSAIDs exhibited potential activity against Aβ fibrils in terms of predicted binding affinity. Sulindac was found to be the most active compound underscoring the contribution of indene methylene substitution, whereas acetaminophen was observed as least active NSAID. General structural requirements for interaction of NSAIDs with Aβ fibril include: aryl/heteroaryl aromatic moiety connected through a linker of 1-2 atoms to a distal aromatic group. Considering these structural requirements and electronic features, new potent agents can be designed and developed as potential Aβ fibril inhibitors for the treatment of AD.

  1. A novel synthesis of octahydropyrido[3,2-c]carbazole framework of aspidospermidine alkaloids and a combined computational, FT-IR, NMR, NBO, NLO, FMO, MEP study of the cis-4a-Ethyl-1-(2hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole

    Science.gov (United States)

    Uludağ, Nesimi; Serdaroğlu, Goncagul; Yinanc, Abdullah

    2018-06-01

    In this study, we performed a novel synthesis of the octahydropyrido[3,2-c]carbazole derivative 6 from 1 in five steps with a 34% overall yield. We also developed a unique compound 2 by a cyclization reaction from the cyanoethylation of compound 1, which is an intermediate step in the synthesis of Aspidospermidine. The parent compound of Aspidospermidine alkaloids, comprise a large family of diverse structures. As a result, we obtained octahydropyrido[3,2-c]carbazole (6)and the proposed method may be applicable to other alkaloids. All quantum chemical calculations of the cis-4a-Ethyl-1-(2-hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole have been performed with the DFT/B3LYP and HF methods by using the Gaussian 09W software package. The most stable conformer obtained from the Potential Energy Surface (PES) scan analysis at the B3LYP/6-31G** level of theory in the gas phase was used as the starting structure of the title compound to further computational analysis. The Natural Bond Orbital (NBO) and NLO analyses were performed to evaluate the intra-molecular interactions contributing to the molecular stability and to predict the optical properties of the title compound, respectively. Gauge-Independent Atomic Orbital (GIAO) approach was used to determine the 1H and 1C NMR chemical shifts of the title compound by subtracting the shielding constants of TMS at both methods. The calculated vibrational frequencies of the title compound were assigned by using the VEDA program and were scaled down by using the scaling factor 0.9668 for B3LYP/6-311++G(d, p) and 0.9050 for HF/6-311++G(d, p) to improve the calculated vibrational frequencies. The FMO (frontier molecular orbital) analysis was evaluated to predict the chemical and physical properties of the title compound and the HOMO, LUMO, and MEP diagrams were visualized by GaussView 4.1 program to present the reactive site of the title compound.

  2. Quantum mechanics study of repulsive π-π interaction and flexibility of phenyl moiety in the iron azodioxide complex

    Science.gov (United States)

    Liu, Yuemin; Liu, Yucheng; Murru, Siva; Tzeng, Nianfeng; Srivastava, Radhey S.

    2015-10-01

    In this study, repulsive π-π interactions within iron azodioxide complex Fe[Ph(O)NN(O)Ph]3 were quantum mechanically characterized using DFT, MP2 and CCSD(T) methods. Flexibility of six phenyl moieties in this complex structure was also investigated by structural optimization approach using the DFT methods. Our MP2 and CCSD(T) calculations of the closest pair provided interaction energy of 6.62 and 8.29 kcal/mol respectively, which indicate a strongest repulsion among these intra-molecular π-π interactions. Interaction energy of the particular π-π pair calculated from 24 hybrid DFT methods ranges from 4.56 kcal/mol from BHandH method to 15.15 kcal/mol from O3LYP method. Cares should be exercised when interpreting interaction energy and geometry optimization from DFT simulation of systems containing π-π interaction. Comparison between the DFT results and the benchmark CCSD(T) results shows that the DFT calculations of π-π interaction are reasonable but still need to be interpreted with caution. Furthermore, MP2 interaction energy of -44.69 kcal/mol between two substituted π systems/phenyl rings Ph(O)N-moieties suggested that above energetically unfavorable π-π interaction can be compensated by the covalent bond N-N in a single ligand Ph(O)NN(O)Ph, which allows for a reasonable stability across the complex molecules. Optimizations of the entire complex molecule using B3LYP and M06HF methods produced a large variation of π-π distances and orientations, which implied that the complex molecule may perform catalysis at room temperature.

  3. A DFT study of methanol adsorption in 8T rings of chabazite

    NARCIS (Netherlands)

    Mihaleva, V.V.; Santen, van R.A.; Jansen, A.P.J.

    2001-01-01

    Hybrid B3LYP and gradient-corrected PW91 functionals were used for studying methanol adsorption on a zeolite cluster consisting of an 8T ring of chabazite. The comparison of the results obtained with PW91 with periodic calculations has shown that the adopted ring is an adequate approximation for the

  4. A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran

    2011-10-15

    The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Experimental (FT-IR and FT-Raman) and theoretical (HF and DFT) investigation, NMR, NBO, electronic properties and frequency estimation analyses on 2,4,5-trichlorobenzene sulfonyl chloride

    Science.gov (United States)

    Gayathri, R.; Arivazhagan, M.

    2012-11-01

    The present work deals with the structural, electronic, and vibrational analyses of the biomolecule 2,4,5-trichlorobenzene sulfonyl chloride (TCBSC). TCBSC is a novel pharmaceutical compound used in dyes, pesticides, pigments, fluorescence brighteners and intermediate for agricultural chemicals in the manufacture of insecticides. Quantum chemical calculation of geometrical structure and energies of TCBSC was carried out by density functional theory (B3LYP) and ab initio (HF) methods at 6-311+G(d,p) and 6-311++G(d,p) standard basis set. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. NMR analysis shows that the isotropic chemical shifts of carbon and hydrogen atom of TCBSC are giving the reasonable shielding to the molecule. Another interesting property shows nonlinear optical (NLO) behavior. Moreover, we have not only simulated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) but also determined the transition state and energy band gap.

  6. On the truncation of the number of excited states in density functional theory sum-over-states calculations of indirect spin spin coupling constants

    DEFF Research Database (Denmark)

    Zarycz, M. Natalia C.; Provasi, Patricio F.; Sauer, Stephan P. A.

    2015-01-01

    of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH4, NH3, H2O, SiH4, PH3, SH2, C2H2, C2H4 and C2H6. The excited (pseudo)states were obtained from TD-DFT calculations with the B3LYP exchange...

  7. Identification of the best DFT functionals for a reliable prediction of lignin vibrational properties

    DEFF Research Database (Denmark)

    Barsberg, Soren

    2015-01-01

    Lignin is the most abundant aromatic plant polymer on earth. Useful information on its structure and interactions is gained by vibrational spectroscopy and relies on the quality of band assignments. B3LYP predictions were recently shown to support band assignments. Further progress calls...

  8. Theoretical Investigation on the Molecular Structure, Vibrational and NMR Spectra of N, N, 4-Tri chlorobenzenesulfonamide

    International Nuclear Information System (INIS)

    Cinar, M.

    2008-01-01

    In the present study, the structural properties of N,N,4-Tri chlorobenzenesulfonamide have been studied extensively using Density Functional Theory (DFT) employing B3LYP exchange correlation. The geometry of the molecule was fully optimized, vibrational spectrum was calculated and fundamental vibrations were assigned based on the scaled theoretical wavenumbers. The 1 H and 13 C nuclear magnetic resonance (NMR) chemical shifts of the compound were calculated using the Gauge-Invariant Atomic Orbital (GIAO) method. To investigate the basis set effects, calculations were performed at the 6-31G(d,p), 6-311G(d,p), 6-31++G(d,p) and 6-311++G(d,p) levels. Finally, geometric parameters, vibrational bands and isotropic chemical shifts were compared with available experimental data of compound. The fully optimized geometry of the molecule was found to be consistent with the X-ray crystal structure. The observed and calculated frequencies and chemical shifts were found to be in very good agreement. The computed results appear that the basis set has slight effect on the molecular geometry of N,N,4-Tri chlorobenzenesulfonamide

  9. Crystallographic, DFT and docking (cathepsin B) studies on an organotellurium(IV) compound

    International Nuclear Information System (INIS)

    Caracelli, Ignez; Maganhi, Stella H.; Zukerman-Schpector, Julio; Sousa Madureira, Lucas; Stefani, Helio A.; Guadagnin, Rafael C.; Tiekink, Edward R.T.

    2016-01-01

    Some biologically active organotellurium compounds exhibit inhibitory potency against cathepsin B. In this study, an alkyl derivative, viz. [CH 3 (CH 2 ) 2 C(I)=C(H)](nBu)TeI 2 , 1, has been structurally characterised by X-ray crystallography and shown to be coordinated within a C 2 I 2 donor set. When the stereochemically active lone pair of electrons is taken into account, a distorted trigonal bipyramidal geometry results with the iodide atoms in axial positions. Both intra- and inter-molecular Te..I interactions are also noted. If all interactions are considered, the coordination geometry is based on a Ψ-pentagonal bipyramidal geometry. An unusual feature of the structure is the curving of the functionalised C 5 chain. This feature has been explored by DFT methods and shown to arise as a result of close C-H..I interactions. A docking study (cathepsin B) was performed to understand the inhibition mechanism and to compare the new results with previous observations. Notably, 1 has the same pose exhibited by analogous biologically active compounds with aryl groups. Thus, the present study suggests that (alkyl) 2 TeX 2 compounds should also be evaluated for biological activity.

  10. Critical Test of Some Computational Chemistry Methods for Prediction of Gas-Phase Acidities and Basicities.

    Science.gov (United States)

    Toomsalu, Eve; Koppel, Ilmar A; Burk, Peeter

    2013-09-10

    Gas-phase acidities and basicities were calculated for 64 neutral bases (covering the scale from 139.9 kcal/mol to 251.9 kcal/mol) and 53 neutral acids (covering the scale from 299.5 kcal/mol to 411.7 kcal/mol). The following methods were used: AM1, PM3, PM6, PDDG, G2, G2MP2, G3, G3MP2, G4, G4MP2, CBS-QB3, B1B95, B2PLYP, B2PLYPD, B3LYP, B3PW91, B97D, B98, BLYP, BMK, BP86, CAM-B3LYP, HSEh1PBE, M06, M062X, M06HF, M06L, mPW2PLYP, mPW2PLYPD, O3LYP, OLYP, PBE1PBE, PBEPBE, tHCTHhyb, TPSSh, VSXC, X3LYP. The addition of the Grimmes empirical dispersion correction (D) to B2PLYP and mPW2PLYP was evaluated, and it was found that adding this correction gave more-accurate results when considering acidities. Calculations with B3LYP, B97D, BLYP, B2PLYPD, and PBE1PBE methods were carried out with five basis sets (6-311G**, 6-311+G**, TZVP, cc-pVTZ, and aug-cc-pVTZ) to evaluate the effect of basis sets on the accuracy of calculations. It was found that the best basis sets when considering accuracy of results and needed time were 6-311+G** and TZVP. Among semiempirical methods AM1 had the best ability to reproduce experimental acidities and basicities (the mean absolute error (mae) was 7.3 kcal/mol). Among DFT methods the best method considering accuracy, robustness, and computation time was PBE1PBE/6-311+G** (mae = 2.7 kcal/mol). Four Gaussian-type methods (G2, G2MP2, G4, and G4MP2) gave similar results to each other (mae = 2.3 kcal/mol). Gaussian-type methods are quite accurate, but their downside is the relatively long computational time.

  11. Intracranial arterial wall imaging using three-dimensional high isotropic resolution black blood MRI at 3.0 Tesla.

    Science.gov (United States)

    Qiao, Ye; Steinman, David A; Qin, Qin; Etesami, Maryam; Schär, Michael; Astor, Brad C; Wasserman, Bruce A

    2011-07-01

    To develop a high isotropic-resolution sequence to evaluate intracranial vessels at 3.0 Tesla (T). Thirteen healthy volunteers and 4 patients with intracranial stenosis were imaged at 3.0T using 0.5-mm isotropic-resolution three-dimensional (3D) Volumetric ISotropic TSE Acquisition (VISTA; TSE, turbo spin echo), with conventional 2D-TSE for comparison. VISTA was repeated for 6 volunteers and 4 patients at 0.4-mm isotropic-resolution to explore the trade-off between SNR and voxel volume. Wall signal-to-noise-ratio (SNR(wall) ), wall-lumen contrast-to-noise-ratio (CNR(wall-lumen) ), lumen area (LA), wall area (WA), mean wall thickness (MWT), and maximum wall thickness (maxWT) were compared between 3D-VISTA and 2D-TSE sequences, as well as 3D images acquired at both resolutions. Reliability was assessed by intraclass correlations (ICC). Compared with 2D-TSE measurements, 3D-VISTA provided 58% and 74% improvement in SNR(wall) and CNR(wall-lumen) , respectively. LA, WA, MWT and maxWT from 3D and 2D techniques highly correlated (ICCs of 0.96, 0.95, 0.96, and 0.91, respectively). CNR(wall-lumen) using 0.4-mm resolution VISTA decreased by 27%, compared with 0.5-mm VISTA but with reduced partial-volume-based overestimation of wall thickness. Reliability for 3D measurements was good to excellent. The 3D-VISTA provides SNR-efficient, highly reliable measurements of intracranial vessels at high isotropic-resolution, enabling broad coverage in a clinically acceptable time. Copyright © 2011 Wiley-Liss, Inc.

  12. Theoretical and vibrational spectroscopic approach to keto-enol tautomerism in methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate

    Science.gov (United States)

    Arı, Hatice; Özpozan, Talat; Büyükmumcu, Zeki; Kabacalı, Yiğit; Saçmaci, Mustafa

    2016-10-01

    A carbamate compound having tricarbonyl groups, methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (BPOC) was investigated from theoretical and vibrational spectroscopic point of view employing quantum chemical methods. Hybrid Density Functionals (B3LYP, X3LYP and B3PW91) with 6-311 G(d,p) basis set were used for the calculations. Rotational barrier and conformational analyses were performed to find the most stable conformers of keto and enol forms of the molecule. Three transition states for keto-enol tautomerism in gas phase were determined. The results of the calculations show that enol-1 form of BPOC is more stable than keto and enol-2 forms. Hydrogen bonding investigation including Natural bond orbital analysis (NBO) for all the tautomeric structures was employed to compare intra-molecular interactions. The energies of HOMO and LUMO molecular orbitals for all tautomeric forms of BPOC were predicted. Normal Coordinate Analysis (NCA) was carried out for the enol-1 to assign vibrational bands of IR and Raman spectra. The scaling factors were calculated as 0.9721, 0.9697 and 0.9685 for B3LYP, X3LYP and B3PW91 methods, respectively. The correlation graphs of experimental versus calculated vibrational wavenumbers were plotted and X3LYP method gave better frequency agreement than the others.

  13. A Dual Band Additively Manufactured 3D Antenna on Package with Near-Isotropic Radiation Pattern

    KAUST Repository

    Su, Zhen

    2018-04-06

    Internet of things (IoT) applications need wireless connectivity on devices with very small footprints, and in RF obscure environments. The antenna for such applications must work on multiple GSM bands (preferred choice for network connectivity), provide near isotropic radiation pattern to maintain orientation insensitive communication, be small in size so that it can be integrated with futuristic miniaturized IoT devices, and be low in cost to be implemented on billions of devices. This paper presents a novel 3D dual band near-isotropic wideband GSM antenna to fulfill these requirements. The antenna has been realized on the package of electronics through additive manufacturing to ensure efficient utilization of available space and lower cost. The proposed antenna consists of a meander line antenna that is folded on the faces of a 3D package with two variations, 0.375λ length for narrowband version and 0.67λ length for the wideband version. Theoretical conditions to achieve near isotropic radiation pattern with bent wire antennas on a 3D surface have been derived. The antenna has been optimized to operate with embedded electronics and a large metallic battery. The antenna provides 8.9% and 34.4% bandwidths, at 900 and 1800 MHz respectively with decent near isotropic radiation behavior.

  14. The physical chemistry of coordinated aqua-, ammine-, and mixed-ligand Co2+ complexes: DFT studies on the structure, energetics, and topological properties of the electron density.

    Science.gov (United States)

    Varadwaj, Pradeep R; Marques, Helder M

    2010-03-07

    Spin-unrestricted DFT-X3LYP/6-311++G(d,p) calculations have been performed on a series of complexes of the form [Co(H(2)O)(6-n)(NH(3))(n)](2+) (n = 0-6) to examine their equilibrium gas-phase structures, energetics, and electronic properties in their quartet electronic ground states. In all cases Co(2+) in the energy-minimised structures is in a pseudo-octahedral environment. The calculations overestimate the Co-O and Co-N bond lengths by 0.04 and 0.08 A, respectively, compared to the crystallographically observed mean values. There is a very small Jahn-Teller distortion in the structure of [Co(H(2)O)(6)](2+) which is in contrast to the very marked distortions observed in most (but not all) structures of this cation that have been observed experimentally. The successive replacement of ligated H(2)O by NH(3) leads to an increase in complex stability by 6 +/- 1 kcal mol(-1) per additional NH(3) ligand. Calculations using UB3LYP give stabilisation energies of the complexes about 5 kcal mol(-1) smaller and metal-ligand bond lengths about 0.005 A longer than the X3LYP values since the X3LYP level accounts for the London dispersion energy contribution to the overall stabilisation energy whilst it is largely missing at the B3LYP level. From a natural population analysis (NPA) it is shown that the formation of these complexes is accompanied by ligand-to-metal charge transfer the extent of which increases with the number of NH(3) ligands in the coordination sphere of Co(2+). From an examination of the topological properties of the electron charge density using Bader's quantum theory of atoms in molecules it is shown that the electron density rho(c) at the Co-O bond critical points is generally smaller than that at the Co-N bond critical points. Hence Co-O bonds are weaker than Co-N bonds in these complexes and the stability increases as NH(3) replaces H(2)O in the metal's coordination sphere. Several indicators, including the sign and magnitude of the Laplacian of the

  15. Nanocompositional Electron Microscopic Analysis and Role of Grain Boundary Phase of Isotropically Oriented Nd-Fe-B Magnets

    Directory of Open Access Journals (Sweden)

    Gregor A. Zickler

    2017-01-01

    Full Text Available Nanoanalytical TEM characterization in combination with finite element micromagnetic modelling clarifies the impact of the grain misalignment and grain boundary nanocomposition on the coercive field and gives guidelines how to improve coercivity in Nd-Fe-B based magnets. The nanoprobe electron energy loss spectroscopy measurements obtained an asymmetric composition profile of the Fe-content across the grain boundary phase in isotropically oriented melt-spun magnets and showed an enrichment of iron up to 60 at% in the Nd-containing grain boundaries close to Nd2Fe14B grain surfaces parallel to the c-axis and a reduced iron content up to 35% close to grain surfaces perpendicular to the c-axis. The numerical micromagnetic simulations on isotropically oriented magnets using realistic model structures from the TEM results reveal a complex magnetization reversal starting at the grain boundary phase and show that the coercive field increases compared to directly coupled grains with no grain boundary phase independently of the grain boundary thickness. This behaviour is contrary to the one in aligned anisotropic magnets, where the coercive field decreases compared to directly coupled grains with an increasing grain boundary thickness, if Js value is > 0.2 T, and the magnetization reversal and expansion of reversed magnetic domains primarily start as Bloch domain wall at grain boundaries at the prismatic planes parallel to the c-axis and secondly as Néel domain wall at the basal planes perpendicular to the c-axis. In summary our study shows an increase of coercive field in isotropically oriented Nd-Fe-B magnets for GB layer thickness > 5 nm and an average Js value of the GB layer < 0.8 T compared to the magnet with perfectly aligned grains.

  16. DFT calculations of the structures and vibrational spectra of the [Fe(bpy){sub 3}]{sup 2+} and [Ru(bpy){sub 3}]{sup 2+} complexes

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Bruce D. [School of Science, University of Greenwich at Medway, Central Avenue, Chatham Maritime, Kent ME4 4TB (United Kingdom); Dines, Trevor J. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)], E-mail: t.j.dines@dundee.ac.uk; Longhurst, Rayne W. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)

    2008-09-03

    Structures of the [M(bpy){sub 3}]{sup 2+} complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy){sub 3}]{sup 2+} which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the {sup 1}E MLCT excited state.

  17. Molecular structure, vibrational spectra and quantum chemical MP2/DFT studies toward the rational design of hydroxyurea imprinted polymer

    Science.gov (United States)

    Prasad, Bhim Bali; Rai, Garima

    2013-03-01

    In this study, both experimental and theoretical vibrational spectra of template (hydroxyurea, HU), monomer (N-(4,6-bisacryloyl amino-[1,3,5] triazine-2-yl-)-acryl amide, TAT), and HU-TAT complexes were compared and these were respectively found to be in good agreement. Binding energies of HU, when complexed with different monomers, were computed using second order Moller Plesset theory (MP2) at 6-311++G(d,p) level both in the gas as well as solution phases. HU is an antineoplastic agent extensively being used in the treatment of polycythaemia Vera and thrombocythemia. It is also used to reduce the frequency of painful attacks in sickle cell anemia. It has antiretroviral property in disease like AIDS. All spectral characterizations were made using Density Functional Theory (DFT) at B3LYP employing 6-31+g(2d, 2p) basis set. The theoretical values for 13C and 1H NMR chemical shifts were found to be in accordance with the corresponding experimental values. Of all different monomers studied for the synthesis of molecularly imprinted polymer (MIP) systems, the monomer TAT (2 mol) was typically found to have a best binding score requisite for complexation with HU (1 mol) at the ground state.

  18. Mechanical properties of non-centrosymmetric CePt3Si and CePt3B

    Science.gov (United States)

    Rogl, G.; Legut, D.; Sýkora, R.; Müller, P.; Müller, H.; Bauer, E.; Puchegger, S.; Zehetbauer, M.; Rogl, P.

    2017-05-01

    Elastic moduli, hardness (both at room temperature) and thermal expansion (4.2-670 K) have been experimentally determined for polycrystalline CePt3Si and its prototype compound CePt3B as well as for single-crystalline CePt3Si. Resonant ultrasound spectroscopy was used to determine elastic properties (Young’s modulus E and Poisson’s ratio ν) via the eigenfrequencies of the sample and the knowledge of sample mass and dimensions. Bulk and shear moduli were calculated from E and ν, and the respective Debye temperatures were derived. In addition, ab initio DFT calculations were carried out for both compounds. A comparison of parameters evaluated from DFT with those of experiments revealed, in general, satisfactory agreement. Positive and negative thermal expansion values obtained from CePt3Si single crystal data are fairly well explained in terms of the crystalline electric field model, using CEF parameters derived recently from inelastic neutron scattering. DFT calculations, in addition, demonstrate that the atomic vibrations keep almost unaffected by the antisymmetric spin-orbit coupling present in systems with crystal structures having no inversion symmetry. This is opposite to electronic properties, where the antisymmetric spin-orbit interaction has shown to distinctly influence features like the superconducting condensate of CePt3Si.

  19. Quantifying the Performances of DFT for Predicting Vibrationally Resolved Optical Spectra: Asymmetric Fluoroborate Dyes as Working Examples.

    Science.gov (United States)

    Bednarska, Joanna; Zaleśny, Robert; Bartkowiak, Wojciech; Ośmiałowski, Borys; Medved', Miroslav; Jacquemin, Denis

    2017-09-12

    This article aims at a quantitative assessment of the performances of a panel of exchange-correlation functionals, including semilocal (BLYP and PBE), global hybrids (B3LYP, PBE0, M06, BHandHLYP, M06-2X, and M06-HF), and range-separated hybrids (CAM-B3LYP, LC-ωPBE, LC-BLYP, ωB97X, and ωB97X-D), in predicting the vibrationally resolved absorption spectra of BF 2 -carrying compounds. To this end, for 19 difluoroborates as examples, we use, as a metric, the vibrational reorganization energy (λ vib ) that can be determined based on the computationally efficient linear coupling model (a.k.a. vertical gradient method). The reference values of λ vib were determined by employing the CC2 method combined with the cc-pVTZ basis set for a representative subset of molecules. To validate the performances of CC2, comparisons with experimental data have been carried out as well. This study shows that the vibrational reorganization energy, involving Huang-Rhys factors and normal-mode frequencies, can indeed be used to quantify the reliability of functionals in the calculations of the vibrational fine structure of absorption bands, i.e., an accurate prediction of the vibrational reorganization energy leads to absorption band shapes better fitting the selected reference. The CAM-B3LYP, M06-2X, ωB97X-D, ωB97X, and BHandHLYP functionals all deliver vibrational reorganization energies with absolute relative errors smaller than 20% compared to CC2, whereas 10% accuracy can be achieved with the first three functionals. Indeed, the set of examined exchange-correlation functionals can be divided into three groups: (i) BLYP, B3LYP, PBE, PBE0, and M06 yield inaccurate band shapes (λ vib,TDDFT poor band topologies (λ vib,TDDFT > λ vib,CC2 ). This study also demonstrates that λ vib can be reliably estimated using the CC2 model and the relatively small cc-pVDZ basis set. Therefore, the linear coupling model combined with the CC2/cc-pVDZ level of theory can be used as a very efficient

  20. Normal co-ordinate analysis, molecular structural, non-linear optical, second order perturbation studies of Tizanidine by density functional theory.

    Science.gov (United States)

    Sheela, N R; Muthu, S; Sampathkrishnan, S; Al-Saadi, Abdulaziz A

    2015-03-15

    The spectroscopic techniques and semi-empirical molecular calculations have been utilized to analyze the drug Tizanidine (5CDIBTA). The solid phase Fourier Transform Infrared (FTIR) and Fourier Transform Raman (FTR) spectral analysis of 5CDIBTA is carried out along with density functional theory (DFT) calculations (B3LYP) with the 6-311++G(d,p) basis set. Detailed interpretation of the vibrational spectra of the compound has been made on the basis of the calculated potential energy distribution (PED). The individual atomic charges by NPA using B3LYP method is studied. A study on the Mulliken atomic charges, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (μ) and the first hyperpolarizability (α) values of the investigated molecule were also computed. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Molecular modeling, FTIR spectral characterization and mechanical properties of carbonated-hydroxyapatite prepared by mechanochemical synthesis

    International Nuclear Information System (INIS)

    Youness, Rasha A.; Taha, Mohammed A.; Elhaes, Hanan; Ibrahim, Medhat

    2017-01-01

    Nanocrystalline B-type carbonate substituted hydroxyapatite (B-CHA) powder has been successively synthesized by mechanochemical method. The effect of milling times on the formation of B-CHA was investigated by Fourier transform infrared spectroscopy, X-ray diffraction technique and scanning electron microscopy. Moreover, physical as well as mechanical properties were examined as a function of milling time. Furthermore, theoretical model was presented for hydroxyapatite (HA). Semiempirical calculations at PM6 level were used to calculate thermal parameters including entropy; enthalpy; heat capacity; free energy and heat of formation in the temperature range from 200 up to 500 k. The results revealed that single phase B-CHA was successfully formed after 8 h of milling when Ball to Powder Ratio (BPR) equals to 10:1. Results revealed that entropy; enthalpy and heat capacity gradually increased as a function of temperature while, free energy and heat of formation decreased with the increasing of temperature. Comparison with higher level of theory was conducted at HF and DFT using the models HF/3-21g**; B3LYP/6-31G(d,p) and B3LYP/LANL2DZ, respectively and indicated that PM6 could be utilized with appropriate accuracy and time to study physical and thermochemical parameters for HA. - Highlights: • Preparation of Nanocrystalline B-type carbonate substituted hydroxyapatite (B-CHA) powder by mechanochemical method. • Characterization of CHA. • Semiemperical and DFT models for CHA.

  2. Molecular modeling, FTIR spectral characterization and mechanical properties of carbonated-hydroxyapatite prepared by mechanochemical synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Youness, Rasha A. [Spectroscopy Department, National Research Centre, El-Bohouth Str., 12622, Dokki, Giza (Egypt); Taha, Mohammed A. [Solid-State Physics Department, National Research Centre, El-Bohouth Str., 12622, Dokki, Giza (Egypt); Elhaes, Hanan [Physics Department, Faculty of Women for Arts, Science, and Education, Ain Shams University, 11757 Cairo (Egypt); Ibrahim, Medhat, E-mail: medahmed6@yahoo.com [Spectroscopy Department, National Research Centre, El-Bohouth Str., 12622, Dokki, Giza (Egypt)

    2017-04-01

    Nanocrystalline B-type carbonate substituted hydroxyapatite (B-CHA) powder has been successively synthesized by mechanochemical method. The effect of milling times on the formation of B-CHA was investigated by Fourier transform infrared spectroscopy, X-ray diffraction technique and scanning electron microscopy. Moreover, physical as well as mechanical properties were examined as a function of milling time. Furthermore, theoretical model was presented for hydroxyapatite (HA). Semiempirical calculations at PM6 level were used to calculate thermal parameters including entropy; enthalpy; heat capacity; free energy and heat of formation in the temperature range from 200 up to 500 k. The results revealed that single phase B-CHA was successfully formed after 8 h of milling when Ball to Powder Ratio (BPR) equals to 10:1. Results revealed that entropy; enthalpy and heat capacity gradually increased as a function of temperature while, free energy and heat of formation decreased with the increasing of temperature. Comparison with higher level of theory was conducted at HF and DFT using the models HF/3-21g**; B3LYP/6-31G(d,p) and B3LYP/LANL2DZ, respectively and indicated that PM6 could be utilized with appropriate accuracy and time to study physical and thermochemical parameters for HA. - Highlights: • Preparation of Nanocrystalline B-type carbonate substituted hydroxyapatite (B-CHA) powder by mechanochemical method. • Characterization of CHA. • Semiemperical and DFT models for CHA.

  3. Synthesis, structural characterization and theoretical studies of a new Schiff base 4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl) imino)methyl)phenol

    Science.gov (United States)

    Cuenú, Fernando; Londoño-Salazar, Jennifer; Torres, John Eduard; Abonia, Rodrigo; D'Vries, Richard F.

    2018-01-01

    4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl)imino)methyl)phenol (4-OHFPz) was synthesized and characterized by FT-IR, MS, NMR, and single-crystal X-ray diffraction. Optimization of molecular geometry, vibrational frequencies, and chemical shifts were calculated by using the methods of density functional theory (DFT) with B3LYP and B3PW91 as functionals and Hartree-Fock with 6-311G++(d,p) as basis set using the GAUSSIAN 09 program package. With the VEDA 4 software, the vibrational frequencies were assigned in terms of the potential energy distribution (PED). The equilibrium geometries calculated by all methods were compared with X-ray diffraction results, indicating that the theoretical results matches well with the experimental ones. The data obtained from the vibrational analysis and the calculated NMR are consistent with the experimental spectra.

  4. Explosive and pollutant TNP detection by structurally flexible SOFs: DFT-D3, TD-DFT study and in vitro recognition

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Pritam [Surface Engineering & Tribology Group, CSIR-Central Mechanical Engineering Research Institute, Mahatma Gandhi Avenue, Burdwan, Durgapur 713209, West Bengal (India); Chemistry Department, Jadavpur University, Kolkata 32, West Bengal (India); Roy, Partha [Chemistry Department, Jadavpur University, Kolkata 32, West Bengal (India); Ghosh, Ananta [Chemistry Department, Burdwan Raj College, The University of Burdwan, West Bengal (India); Jana, Saibal [Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Murmu, Naresh Chandra [Surface Engineering & Tribology Group, CSIR-Central Mechanical Engineering Research Institute, Mahatma Gandhi Avenue, Burdwan, Durgapur 713209, West Bengal (India); Mukhopadhyay, Subhra Kanti [Department of Microbiology, The University of Burdwan, Burdwan 713104 (India); Banerjee, Priyabrata, E-mail: pr_banerjee@cmeri.res.in [Surface Engineering & Tribology Group, CSIR-Central Mechanical Engineering Research Institute, Mahatma Gandhi Avenue, Burdwan, Durgapur 713209, West Bengal (India); Academy of Scientific and Innovative Research at CSIR-Central Mechanical Engineering Research Institute (CMERI), Mahatma Gandhi Avenue, Durgapur 713209, West Bengal (India)

    2017-05-15

    Explosive and Pollutant Nitro Aromatics (epNACs) like 2,4,6-trinitrophenol (TNP) has been detected from various surface water specimens by luminescent Schiff base Organic Frameworks (SOFs) by fluorometric method. Fluorescence intensity of the receptor SOFs have been quenched in presence of TNP due to RET and ICT, which has been confirmed through solid and solution level spectroscopic studies like FT-IR, {sup 1}H-NMR, fluorescence titration. Modern DFT (DFT-D3) calculations of the possible host guest conformers have been performed for exploration of plausible route of interaction between receptor and epNACs. The outcome of theoretical calculations is in line with experimental findings where TNP and receptor conformation mimic parallel displaced type π- π interaction. TD-DFT has been executed with both receptor and receptor ···TNP adduct, the fluorescence quenching is in line with experimental outcome. Limit of TNP detection has been found as low as 5 μM with 2.97×10{sup 4} M{sup -1} as binding constant. In real time stepping, TNP as mutagenic agent for aquatic life has been detected inside prokaryotic cells like candidia albicans in ppm level.

  5. Structural, spectroscopic (FT-IR, NMR, UV-visible), nonlinear optical (NLO), cytotoxic and molecular docking studies of 4-nitro-isonitrosoacetophenone (ninapH) by DFT method

    Science.gov (United States)

    Kucuk, Ilhan; Kaya, Yunus; Kaya, A. Asli

    2017-07-01

    (4-Nitro-phenyl)-oxo-acetaldehyde oxime (ninapH) is a type of oxime, which has a oxime and α-carbonyl groups. This molecule has been synthesized from literature procedure. The structural properties and conformational behaviors were examined using the density functional theory (DFT) with the B3LYP method combined with the 6-311++G(d,p) basis set. As a result of the conformational studies, the most stable conformer was determined, and then this molecule was optimized with the same basis set. Comprehensive theoretical and experimental structural studies on the molecule have been carried out by FT-IR, NMR and UV-vis spectrometry. The calculated HOMO and LUMO energies show that charge transfer within the molecule. The first order hyperpolarizability and molecular electrostatic potential (MEP) were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the ninapH have been calculated at different temperatures, 100-1000 K. In addition, the molecular docking studies have been performed with DNA and protein structures (downloaded from Protein Data Bank).

  6. Infrared, Raman and density functional characterization and structural study of 2-Nitro-2-phenyl-propane-1,3-diol

    Science.gov (United States)

    Kaya, Mehmet Fatih; Bağlayan, Özge; Kaya, Esma Güneş; Alver, Özgür

    2017-12-01

    Nitro compound and nitro derivatives are industrially important to produce rubber and agricultural chemicals. In this study, one of the promising derivatives of nitro compound 2-Nitro-2-phenyl-propane-1,3-diol (2NPP) is examined in detail. FT-Infrared and dispersive Raman spectra of 2NPP (C9H11NO4) were respectively recorded in 4000-10 cm-1 and 4000-100 cm-1. The bond distances and angles, conformational distributions, vibrational frequencies and the assignment of each mode, some thermodynamic parameters and reactivity descriptors: total energy, hardness, chemical potential, electrophilicity index, electronegativity, frontier orbitals energy gap of 2NPP were investigated by using DFT/B3LYP method with 6-31++G (d,p) basis set. In order to locate the global minimum on the potential energy surface of 2NPP, a beforehand conformational examinations were carried out using Spartan 10 along with semi-emprical PM6 method. The results of conformational analyses showed that there are five possible conformations having energies under 2 kcal/mol. Comparison of the theoretical and experimental results clearly indicates that density functional hybrid B3LYP/6-31++G (d,p) level of theory can be used to predict vibrational frequencies and structural parameters of 2NPP. Further, C1 geometry is considered to be the global minimum conformation of 2NPP.

  7. Tuning the NLO properties of polymethineimine chains by chemical substitution

    International Nuclear Information System (INIS)

    Medved’, Miroslav; Jacquemin, Denis

    2013-01-01

    Highlights: ► Properties of the most stable isomers of polymethineimine (PMI) are investigated. ► 2nd order NLO properties of experimentally known PMI derivatives are determined. ► Structure-property relationships are unraveled for several series of oligomers. ► Performance of long-range corrected DFT methods is assessed. - Abstract: Structure and molecular electronic properties including dipole moment, polarizability and first hyperpolarizability of polymethineimine (PMI) oligomers (up to hexadecamers) and its experimentally known amino-, methyl-, and cyano-derivatives are investigated using several ab initio methods (HF, MP2 and DFT). It is shown that side-chain substitutions have significant effects both on the structure and molecular properties of PMI chains. Depending on the substitution, two types of structures have been identified. The first is characterized by a bent skeleton and encompasses PMI, polyacetonitrile (PAcN), and polycyanonitrile (PCN). The second, represented by polyaminonitrile (PAN), remains quasi-linear with the plane of the unit cell (UC) only slightly rotating around the longitudinal molecular axis. These structural differences are also reflected in molecular properties; while in case of PMI, PAcN, and PCN the longitudinal component of properties (reduced per UC) reaches its maximum value for medium-size oligomers and then decreases for longer chains, the linear and nonlinear properties of PAN steadily increase towards the polymeric limit. In addition, we have assessed the performances of long-range corrected DFT functionals (LR-DFT), namely LC-BLYP, CAM-B3LYP, and ωB97X within the present framework: they provide results in qualitative agreement with MP2, a success not reached with B3LYP

  8. Hydroxylated crystalline edingtonite silica faces as models for the amorphous silica surface

    Energy Technology Data Exchange (ETDEWEB)

    Tosoni, S; Civalleri, B; Ugliengo, P [Dipartimento di Chimica IFM and NIS (Centre of Excellence), Universita di Torino, Via P. Giuria 7, 10125 Torino - ITALY (Italy); Pascale, F [Laboratoire de Cristallographie ed Modelisation des Materiaux Mineraux et Biologiques, UMR-CNRS-7036. Universite Henri Poincare - Nancy I, B.P. 239, 54506 Vandoeuvre-les-Nancy Cedex 05 - FRANCE (France)], E-mail: piero.ugliengo@unito.it

    2008-06-01

    Fully hydroxylated surfaces derived from crystalline edingtonite were adopted to model the variety of sites known to exist at the amorphous silica surface, namely isolated, geminal and interacting silanols. Structures, energetics and vibrational features of the surfaces either bare or in contact with water were modelled at DFT level using the B3LYP functional with a GTO basis set of double-zeta polarized quality using the periodic ab-initio CRYSTAL06 code. Simulated infrared spectra of both dry and water wet edingtonite surfaces were in excellent agreement with the experimental ones recorded on amorphous silica. Water interaction energies were compared with microcalorimetric differential heats of adsorption data showing good agreement, albeit computed ones being slightly underestimated due to the lack of dispersive forces in the B3LYP functional.

  9. An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

    Science.gov (United States)

    Song, Y. Z.; Wei, K. X.; Lv, J. S.

    2013-12-01

    DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

  10. Photoelectron and UV absorption spectroscopy for determination of electronic configurations of negative molecular ions: Chlorophenols

    International Nuclear Information System (INIS)

    Tseplin, E.E.; Tseplina, S.N.; Tuimedov, G.M.; Khvostenko, O.G.

    2009-01-01

    The photoelectron and UV absorption spectra of p-, m-, and o-chlorophenols in the gas phase have been obtained. On the basis of DFT B3LYP/6-311++G(d, p) calculations, the photoelectron bands have been assigned to occupied molecular orbitals. From the TDDFT B3LYP/6-311++G(d, p) calculation results, the UV absorption bands have been assigned to excited singlet states of the molecules under investigation. For each excited state a dominant transition was found. It has been shown that the energies of these singlet transitions correlate with the energy differences between the ground-state molecular orbitals participating in them. Using the UV spectra interpretation, the electronic states of molecular anions detected earlier for the same compounds by means of the resonant electron capture mass-spectrometry have been determined.

  11. G3//BMK and Its Application to Calculation of Bond Dissociation Enthalpies.

    Science.gov (United States)

    Zheng, Wen-Rui; Fu, Yao; Guo, Qing-Xiang

    2008-08-01

    On the basis of systematic examinations it was found that the BMK functional significantly outperformed the other popular density functional theory methods including B3LYP, B3P86, KMLYP, MPW1P86, O3LYP, and X3LYP for the calculation of bond dissociation enthalpies (BDEs). However, it was also found that even the BMK functional might dramatically fail in predicting the BDEs of some chemical bonds. To solve this problem, a new composite ab initio method named G3//BMK was developed by combining the strengths of both the G3 theory and BMK. G3//BMK was found to outperform the G3 and G3//B3LYP methods. It could accurately predict the BDEs of diverse types of chemical bonds in various organic molecules within a precision of ca. 1.2 kcal/mol.

  12. Selective synthesis, structural studies and antitumor evaluation of some novel unsymmetrical 1-hetaryl-4-(2-chloroquinolin-3-ylazines

    Directory of Open Access Journals (Sweden)

    Samir Bondock

    2016-11-01

    Full Text Available A series of novel unsymmetrical 1-hetaryl-4-(2-chloroquinolin-3-yl azines 4–9 was selectively synthesized in a three-step procedure starting from acetanilide (1. The molecular structures of 4–9 were established by elemental analyses, spectral data, hybrid density functional theory (DFT and time-dependent density functional theory (TD-DFT calculations. Molecular conformation analysis for compounds 4–9, performed using DFT calculations utilizing the energy functional 3-Parameter (Exchange, Lee, Yang and Parr (B3LYP and the full-electron basis set Density Gauss double-zeta with polarization functions (DGDZVP, on the synthesized azines considering the torsion angles (θ1, θ2, θ3 revealed 8 plausible conformers for each compound. Electronic and thermodynamic properties including the dipole moment and the thermodynamic energy values of the Frontier occupied and virtual molecular orbitals, HOMO and LUMO, respectively, were calculated for the most stable conformer for each compound. Furthermore, TD-DFT calculations coupled with the polarizable conductor calculation model (PCM, performed on the most stable conformers in DMF to account for the solvent effect, revealed that the optical properties including λmax and oscillator strength performed on the most stable conformers were in excellent agreement with the experimental λmax and molar extinction coefficient, which clearly validate the most stable molecular conformers identified for compounds 4–9. Comparison of the biological results to the calculated electronic and thermodynamic properties showed that the cytotoxicity is dependent on the low-lying ELUMO because compound 8 has the lowest ELUMO value and exhibited the greatest antitumor activity.

  13. Molecular structure, vibrational analysis (IR and Raman) and quantum chemical investigations of 1-aminoisoquinoline

    Science.gov (United States)

    Sivaprakash, S.; Prakash, S.; Mohan, S.; Jose, Sujin P.

    2017-12-01

    Quantum chemical calculations of energy and geometrical parameters of 1-aminoisoquinoline [1-AIQ] were carried out by using DFT/B3LYP method using 6-311G (d,p), 6-311G++(d,p) and cc-pVTZ basis sets. The vibrational wavenumbers were computed for the energetically most stable, optimized geometry. The vibrational assignments were performed on the basis of potential energy distribution (PED) using VEDA program. The NBO analysis was done to investigate the intra molecular charge transfer of the molecule. The frontier molecular orbital (FMO) analysis was carried out and the chemical reactivity descriptors of the molecule were studied. The Mulliken charge analysis, molecular electrostatic potential (MEP), HOMO-LUMO energy gap and the related properties were also investigated at B3LYP level. The absorption spectrum of the molecule was studied from UV-Visible analysis by using time-dependent density functional theory (TD-DFT). Fourier Transform Infrared spectrum (FT-IR) and Raman spectrum of 1-AIQ compound were analyzed and recorded in the range 4000-400 cm-1 and 3500-100 cm-1 respectively. The experimentally determined wavenumbers were compared with those calculated theoretically and they complement each other.

  14. Vibrational spectroscopy investigation using ab initio and density functional theory analysis on the structure of 3-(6-benzoyl-2-oxobenzo[ d]oxazol-3(2 H)-yl)propanoic acid

    Science.gov (United States)

    Arslan, Hakan; Algül, Öztekin; Önkol, Tijen

    2008-08-01

    The molecular structure, vibrational frequencies and infrared intensities of the 3-(6-benzoyl-2-oxobenzo[ d]oxazol-3(2 H)-yl)propanoic acid were calculated by the HF and DFT methods using 6-31G(d) basis set. The FT-infrared spectra have been measured for the title compound in the solid state. We obtained 11 stable conformers for the title compound, however the Conformer 1 is approximately 3.88 kcal/mol more stable than the Conformer 11. The comparison of the theoretical and experimental geometry of the title compound shows that the X-ray parameters fairly well reproduce the geometry of the Conformer 1. The harmonic vibrations computed of this compound by the B3LYP/6-31G(d) method are in a good agreement with the observed IR spectral data. Theoretical vibrational spectra of the title compound were interpreted by means of PEDs using VEDA 4 program.

  15. Molecular structure, vibrational spectroscopic analysis (IR & Raman), HOMO-LUMO and NBO analysis of anti-cancer drug sunitinib using DFT method

    Science.gov (United States)

    Mıhçıokur, Özlem; Özpozan, Talat

    2017-12-01

    Oxindole and its derivatives have wide applications in different industries such as in synthetic & natural fibers, dyes for hair and plastic materials in addition to their biological importance. In the present study, one of the oxindole derivatives, N-(2-diethylaminoethyl)-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide (Sunitinib), which is used as an anti-cancer drug, was investigated in terms of structural, vibrational spectroscopic and theoretical analysis. The calculations have been performed for gaseous, aqueous and DMSO phases, respectively. Potential Energy Surface (PES) scan has been carrried out to obtain the most stable structures of all the phases of the title molecule using B3LYP/6-31G(d,p) level and the geometrical variations among them are discussed. The solvent effect for Sunitinib in aqueous and DMSO phases have been performed by means of the self-consistent recognition reaction field (SCRF) method as implemented in the integral equation formalism polarized continuum model (IEFPCM). On the other hand, NBO analysis has been carried out to understand probable hydrogen bonding sites and charge transfers. Additionally, the HOMO and the LUMO energies are calculated using B3LYP/6-31G(d,p) to determine the intra molecular charge transfers (ICT) within the molecule and the kinetic stabilities for each phases. The molecular electrostatic potential surface (MESP) has been plotted over the optimized structure to estimate the reactive sites of electrophilic and nucleophilic attacks regarding Sunitinib molecule. The potential energy distribution (PED) has been calculated using VEDA4 program and vibrational assignments of the experimental spectra (IR & Raman) have been elucidated by means of the calculated vibrational spectra. The observed vibrational spectra of Sunitinib is compared with the calculated spectra obtained by using B3LYP functional both with 6-31G(d,p) and 6-311++G(d,p) basis sets. Theoretical results

  16. Computational and Experimental Study on Molecular Structure of Benzo[g]pyrimido[4,5-b]quinoline Derivatives: Preference of Linear over the Angular Isomer

    Directory of Open Access Journals (Sweden)

    Jorge Trilleras

    2017-09-01

    Full Text Available A series of 5-aryl-2-methylthio-5,12-dihydrobenzo[g]pyrimido[4,5-b]quinoline-4,6,11(3H-trione was synthesized through an environmental friendly multicomponent methodology and characterized with FT-IR (Fourier Transform infrared spectroscopy, 1H NMR (Nuclear Magnetic Resonance , 13C NMR and GC-MS (gas chromatography-mass spectrometry. The 5-(4-methoxyphenyl-2-methylthio-5,12-dihydrobenzo[g]pyrimido[4,5-b]quinoline-4,6,11(3H-trione 4c compound was characterized by X-ray single crystal diffraction. The geometry of 4c has been fully optimized using DFT (Density functional theory, B3LYP functional and 6-31G(d,p basis set, thus establishing the ground state energy and thermodynamic features for the mentioned compound, which are in accordance with the experimental data and the crystal structure. The experimental results reveal a strong preference for the regioselective formation of 4c linear four fused rings over the angular four fused and suggest a possible kinetic control in product formation.

  17. Substitution Structures of Large Molecules and Medium Range Correlations in Quantum Chemistry Calculations

    Science.gov (United States)

    Evangelisti, Luca; Pate, Brooks

    2017-06-01

    A study of the minimally exciting topic of agreement between experimental and measured rotational constants of molecules was performed on a set of large molecules with 16-18 heavy atoms (carbon and oxygen). The molecules are: nootkatone (C_{15}H_{22}O), cedrol (C_{15}H_{26}O), ambroxide (C_{16}H_{28}O), sclareolide (C_{16}H_{22}O_{2}), and dihydroartemisinic acid (C_{15}H_{24}O_{2}). For this set of molecules we obtained 13C-subsitution structures for six molecules (this includes two conformers of nootkatone). A comparison of theoretical structures and experimental substitution structures was performed in the spirit of the recent work of Grimme and Steinmetz.[1] Our analysis focused the center-of-mass distance of the carbon atoms in the molecules. Four different computational methods were studied: standard DFT (B3LYP), dispersion corrected DFT (B3LYP-D3BJ), hybrid DFT with dispersion correction (B2PLYP-D3), and MP2. A significant difference in these theories is how they handle medium range correlation of electrons that produce dispersion forces. For larger molecules, these dispersion forces produce an overall contraction of the molecule around the center-of-mass. DFT poorly treats this effect and produces structures that are too expanded. MP2 calculations overestimate the correction and produce structures that are too compact. Both dispersion corrected DFT methods produce structures in excellent agreement with experiment. The analysis shows that the difference in computational methods can be described by a linear error in the center-of-mass distance. This makes it possible to correct poorer performing calculations with a single scale factor. We also reexamine the issue of the "Costain error" in substitution structures and show that it is significantly larger in these systems than in the smaller molecules used by Costain to establish the error limits. [1] Stefan Grimme and Marc Steinmetz, "Effects of London dispersion correction in density functional theory on

  18. Theoretical and spectroscopic studies of a tricyclic antidepressant, imipramine hydrochloride

    Science.gov (United States)

    Sagdinc, S. G.; Azkeskin, Caner; Eşme, A.

    2018-06-01

    Imipramine hydrochloride ([H-IMI]Cl), C19H24N2.HCl, is the prototypic tricyclic antidepressant (TCA) inhibitor of norepinephrine and serotonin neuronal reuptake. The molecular structure, molecular electrostatic potential (MEP), natural bond orbital (NBO) analysis, linear and non-linear optical (NLO) properties of [H-IMI]Cl have been investigated using the density functional theory (DFT) calculations with the B3LYP level at the 6‒311++G(d,p) basis set. The UV-Vis spectra for [H-IMI]Cl were experimentally studied in water and methanol. TD‒DFT calculations in water and methanol were employed to investigate the absorption wavelengths (λ), excitation energies (E), and oscillator strengths (f) for the UV-Vis analysis and the major contributions to the electronic transitions. From NBO analysis, the orbitals with the stabilization energy E(2) of 192.15 kcal/mol are π*(C5sbnd C18) as donor NBO and π*(C19sbnd C20) as acceptor NBO. The FT‒IR (4000‒400 cm-1) and FT‒Raman (3500-50 cm-1) spectra have been measured and analyzed. The assignment of bands observed vibrational spectra have been made by comparison of its calculated theoretical vibrational frequencies obtained using the DFT/B3LYP/6‒311++G(d,p) method. The detailed vibrational assignments were performed with the DFT calculation, and the potential energy distribution (PED) of [H-IMI]Cl was obtained by the Vibrational Energy Distribution Analysis 4 (VEDA4) program. The scaled frequencies resulted in good agreement with the observed spectral patterns.

  19. Prediction of core level binding energies in density functional theory: Rigorous definition of initial and final state contributions and implications on the physical meaning of Kohn-Sham energies.

    Science.gov (United States)

    Pueyo Bellafont, Noèlia; Bagus, Paul S; Illas, Francesc

    2015-06-07

    A systematic study of the N(1s) core level binding energies (BE's) in a broad series of molecules is presented employing Hartree-Fock (HF) and the B3LYP, PBE0, and LC-BPBE density functional theory (DFT) based methods with a near HF basis set. The results show that all these methods give reasonably accurate BE's with B3LYP being slightly better than HF but with both PBE0 and LCBPBE being poorer than HF. A rigorous and general decomposition of core level binding energy values into initial and final state contributions to the BE's is proposed that can be used within either HF or DFT methods. The results show that Koopmans' theorem does not hold for the Kohn-Sham eigenvalues. Consequently, Kohn-Sham orbital energies of core orbitals do not provide estimates of the initial state contribution to core level BE's; hence, they cannot be used to decompose initial and final state contributions to BE's. However, when the initial state contribution to DFT BE's is properly defined, the decompositions of initial and final state contributions given by DFT, with several different functionals, are very similar to those obtained with HF. Furthermore, it is shown that the differences of Kohn-Sham orbital energies taken with respect to a common reference do follow the trend of the properly calculated initial state contributions. These conclusions are especially important for condensed phase systems where our results validate the use of band structure calculations to determine initial state contributions to BE shifts.

  20. Molecular design of new hydrazone dyes for dye-sensitized solar cells: Synthesis, characterization and DFT study

    KAUST Repository

    Al-Sehemi, Abdullah G.; Irfan, Ahmad; Asiri, Abdullah M.; Ammar, Yousry Ahmed

    2012-01-01

    }ethylene-1,1,2-tricarbonitrile (BBHPET) have been synthesized. The dyes showed pronounced solvatochromic effects as the polarity of the solvents increased. The structures have been optimized at B3LYP/6-31G(d) level of theory. The torsion in E

  1. Electronic spectra and DFT calculations of some pyrimido[1,2-a]benzimidazole derivatives

    Science.gov (United States)

    Elshakre, Mohamed E.; Moustafa, H.; Hassaneen, Huwaida. M. E.; Moussa, Abdelrahim. Z.

    2015-06-01

    Ground state properties of 2,4-diphenyl-1,4-dihydrobenzo[4,5]imidazo[1,2-a]pyrimidine, compound 1, and its derivatives are investigated experimentally and theoretically in Dioxane and DMF. The calculations show that all the studied compounds (1-7) are non-planar, resulting in a significant impact on the electronic and structural properties. The ground state properties of compounds 1-7 at B3LYP/6-311G (d, p) show that compound 5 has the lowest EHOMO, ELUMO, and ΔE indicating highest reactivity. Compound 7 is found to have the highest polarity. The observed UV spectra in Dioxane and DMF of compounds 1-4 show 2 bands, while compounds 5-7 show 4 bands in both solvents. Band maxima (λmax) and intensities of the spectra are found to have solvent dependence reflected as blue and red shifts. The theoretical spectra computed at TD-B3LYP/6-311G (d, p) in gas phase, Dioxane and DMF indicate a good agreement with the observed spectra.

  2. The isotropic radio background revisited

    Energy Technology Data Exchange (ETDEWEB)

    Fornengo, Nicolao; Regis, Marco [Dipartimento di Fisica Teorica, Università di Torino, via P. Giuria 1, I–10125 Torino (Italy); Lineros, Roberto A. [Instituto de Física Corpuscular – CSIC/U. Valencia, Parc Científic, calle Catedrático José Beltrán, 2, E-46980 Paterna (Spain); Taoso, Marco, E-mail: fornengo@to.infn.it, E-mail: rlineros@ific.uv.es, E-mail: regis@to.infn.it, E-mail: taoso@cea.fr [Institut de Physique Théorique, CEA/Saclay, F-91191 Gif-sur-Yvette Cédex (France)

    2014-04-01

    We present an extensive analysis on the determination of the isotropic radio background. We consider six different radio maps, ranging from 22 MHz to 2.3 GHz and covering a large fraction of the sky. The large scale emission is modeled as a linear combination of an isotropic component plus the Galactic synchrotron radiation and thermal bremsstrahlung. Point-like and extended sources are either masked or accounted for by means of a template. We find a robust estimate of the isotropic radio background, with limited scatter among different Galactic models. The level of the isotropic background lies significantly above the contribution obtained by integrating the number counts of observed extragalactic sources. Since the isotropic component dominates at high latitudes, thus making the profile of the total emission flat, a Galactic origin for such excess appears unlikely. We conclude that, unless a systematic offset is present in the maps, and provided that our current understanding of the Galactic synchrotron emission is reasonable, extragalactic sources well below the current experimental threshold seem to account for the majority of the brightness of the extragalactic radio sky.

  3. The isotropic radio background revisited

    International Nuclear Information System (INIS)

    Fornengo, Nicolao; Regis, Marco; Lineros, Roberto A.; Taoso, Marco

    2014-01-01

    We present an extensive analysis on the determination of the isotropic radio background. We consider six different radio maps, ranging from 22 MHz to 2.3 GHz and covering a large fraction of the sky. The large scale emission is modeled as a linear combination of an isotropic component plus the Galactic synchrotron radiation and thermal bremsstrahlung. Point-like and extended sources are either masked or accounted for by means of a template. We find a robust estimate of the isotropic radio background, with limited scatter among different Galactic models. The level of the isotropic background lies significantly above the contribution obtained by integrating the number counts of observed extragalactic sources. Since the isotropic component dominates at high latitudes, thus making the profile of the total emission flat, a Galactic origin for such excess appears unlikely. We conclude that, unless a systematic offset is present in the maps, and provided that our current understanding of the Galactic synchrotron emission is reasonable, extragalactic sources well below the current experimental threshold seem to account for the majority of the brightness of the extragalactic radio sky

  4. Macroscopic simulation of isotropic permanent magnets

    International Nuclear Information System (INIS)

    Bruckner, Florian; Abert, Claas; Vogler, Christoph; Heinrichs, Frank; Satz, Armin; Ausserlechner, Udo; Binder, Gernot; Koeck, Helmut; Suess, Dieter

    2016-01-01

    Accurate simulations of isotropic permanent magnets require to take the magnetization process into account and consider the anisotropic, nonlinear, and hysteretic material behaviour near the saturation configuration. An efficient method for the solution of the magnetostatic Maxwell equations including the description of isotropic permanent magnets is presented. The algorithm can easily be implemented on top of existing finite element methods and does not require a full characterization of the hysteresis of the magnetic material. Strayfield measurements of an isotropic permanent magnet and simulation results are in good agreement and highlight the importance of a proper description of the isotropic material. - Highlights: • Simulations of isotropic permanent magnets. • Accurate calculation of remanence magnetization and strayfield. • Comparison with strayfield measurements and anisotropic magnet simulations. • Efficient 3D FEM–BEM coupling for solution of Maxwell equations.

  5. Multi-contrast, isotropic, single-slab 3D MR imaging in multiple sclerosis

    NARCIS (Netherlands)

    Moraal, Bastiaan; Roosendaal, Stefan; Pouwels, Petra; Vrenken, Hugo; Schijndel, van Ronald; Meier, Dominik; Guttmann, Charles; Geurts, Jeroen; Barkhof, Frederik

    2008-01-01

    To describe signal and contrast properties of an isotropic, single-slab 3D dataset [double inversion- recovery (DIR), fluid-attenuated inversion recovery (FLAIR), T2, and T1-weighted magnetization prepared rapid acquisition gradient-echo (MPRAGE)] and to evaluate its performance in detecting

  6. Electronic properties and optical absorption of graphene-polyvinylidene fluoride nanocomposites: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Chopra, Siddheshwar, E-mail: schopra1@amity.edu

    2017-01-15

    Graphene/polyvinylidene fluoride (graphene/PVDF) nanocomposites were studied using Density functional theory (DFT)/Time dependent density functional theory (TDDFT) calculations. Five nanocomposite configurations were constructed. Electronic properties like binding energy, electronic gap and work function were calculated. The most stable structure was determined. The electronic gap of graphene shifts from semiconducting to conducting, on nanocomposite formation. Workfunction of the most stable nanocomposite was 4.34eV ± 0.05eV, close to that of the pristine graphene (4.33eV ± 0.05eV). Thermochemical analysis showed that the adsorption is spontaneous above ∼870 K, and endothermic in nature. TDDFT calculations were performed for B3LYP, LSDA, BHHLYP and PBE0 functionals. B3LYP and PBE0 are suitable in describing optical absorption. Optical gap of graphene shrinks, and light absorption gets enhanced on nanocomposite formation. - Highlights: • Various properties of graphene-PVDF nanocomposites were studied theoretically. • Electronic gap of graphene shifts to conducting nature, on composite formation. • Adsorption is spontaneous above ∼870 K, and endothermic in nature. • B3LYP and PBE0 functionals are suitable in describing absorption. • Optical absorption gets enhanced on nanocomposite formation.

  7. Electronic properties and optical absorption of graphene-polyvinylidene fluoride nanocomposites: A theoretical study

    International Nuclear Information System (INIS)

    Chopra, Siddheshwar

    2017-01-01

    Graphene/polyvinylidene fluoride (graphene/PVDF) nanocomposites were studied using Density functional theory (DFT)/Time dependent density functional theory (TDDFT) calculations. Five nanocomposite configurations were constructed. Electronic properties like binding energy, electronic gap and work function were calculated. The most stable structure was determined. The electronic gap of graphene shifts from semiconducting to conducting, on nanocomposite formation. Workfunction of the most stable nanocomposite was 4.34eV ± 0.05eV, close to that of the pristine graphene (4.33eV ± 0.05eV). Thermochemical analysis showed that the adsorption is spontaneous above ∼870 K, and endothermic in nature. TDDFT calculations were performed for B3LYP, LSDA, BHHLYP and PBE0 functionals. B3LYP and PBE0 are suitable in describing optical absorption. Optical gap of graphene shrinks, and light absorption gets enhanced on nanocomposite formation. - Highlights: • Various properties of graphene-PVDF nanocomposites were studied theoretically. • Electronic gap of graphene shifts to conducting nature, on composite formation. • Adsorption is spontaneous above ∼870 K, and endothermic in nature. • B3LYP and PBE0 functionals are suitable in describing absorption. • Optical absorption gets enhanced on nanocomposite formation.

  8. Crystallographic, DFT and docking (cathepsin B) studies on an organotellurium(IV) compound

    Energy Technology Data Exchange (ETDEWEB)

    Caracelli, Ignez; Maganhi, Stella H. [Univ. Federal de Sao Carlos (Brazil). BioMat; Zukerman-Schpector, Julio; Sousa Madureira, Lucas [Univ. Federal de Sao Carlos (Brazil). Lab. de Cristalografia, Estereodinamica e Modelagem Molecular; Stefani, Helio A. [Sao Paulo Univ. (Brazil). Dept. de Farmacia; Guadagnin, Rafael C. [Univ. Federal de Sao Paulo, Diadema (Brazil). Inst. e Ciencias Mabientais, Quimicas e Farmaceuticas; Tiekink, Edward R.T. [Sunway Univ., Selangor Darul Ehsan (Malaysia). Centre for Crystalline Materials

    2016-08-01

    Some biologically active organotellurium compounds exhibit inhibitory potency against cathepsin B. In this study, an alkyl derivative, viz. [CH{sub 3}(CH{sub 2}){sub 2}C(I)=C(H)](nBu)TeI{sub 2}, 1, has been structurally characterised by X-ray crystallography and shown to be coordinated within a C{sub 2}I{sub 2} donor set. When the stereochemically active lone pair of electrons is taken into account, a distorted trigonal bipyramidal geometry results with the iodide atoms in axial positions. Both intra- and inter-molecular Te..I interactions are also noted. If all interactions are considered, the coordination geometry is based on a Ψ-pentagonal bipyramidal geometry. An unusual feature of the structure is the curving of the functionalised C{sub 5} chain. This feature has been explored by DFT methods and shown to arise as a result of close C-H..I interactions. A docking study (cathepsin B) was performed to understand the inhibition mechanism and to compare the new results with previous observations. Notably, 1 has the same pose exhibited by analogous biologically active compounds with aryl groups. Thus, the present study suggests that (alkyl){sub 2}TeX{sub 2} compounds should also be evaluated for biological activity.

  9. Modelling of Octahedral Manganese II Complexes with Inorganic Ligands: A Problem with Spin-States

    Directory of Open Access Journals (Sweden)

    Ludwik Adamowicz

    2003-08-01

    Full Text Available Abstract: Quantum mechanical ab initio UHF, MP2, MC-SCF and DFT calculations with moderate Gaussian basis sets were performed for MnX6, X = H2O, F-, CN-, manganese octahedral complexes. The correct spin-state of the complexes was obtained only when the counter ions neutralizing the entire complexes were used in the modelling at the B3LYP level of theory.

  10. Continuous Chemistry in Ice Cores

    DEFF Research Database (Denmark)

    Kjær, Helle Astrid

    on parameters involved in the study of photolysis as a source of in situ CO2. The concentration of organic substances in Greenland ice is poorly known due to their low levels and the fact that only a few studies evaluate the concentrations of specific organic compounds. Light does not penetrate deep...... depth was found as a function of wavelength. Further, by computational chemistry hybrid density functional methods (DFT), the four most common conformers of pyruvic acid were investigated in both gas, water and ice using the DFT model CAM-B3LYP with dielectric medium methods. A de rease of the energy...

  11. Multi-contrast, isotropic, single-slab 3D MR imaging in multiple sclerosis

    NARCIS (Netherlands)

    Moraal, B.; Roosendaal, S.D.; Pouwels, P.J.W.; Vrenken, H.; van Schijndel, R.A.; Meier, D.S.; Guttmann, C.R.G.; Geurts, J.J.G.; Barkhof, F.

    2008-01-01

    To describe signal and contrast properties of an isotropic, single-slab 3D dataset [double inversion-recovery (DIR), fluid-attenuated inversion recovery (FLAIR), T2, and T1-weighted magnetization prepared rapid acquisition gradient-echo (MPRAGE)] and to evaluate its performance in detecting multiple

  12. DFT calculations, spectroscopic, thermal analysis and biological activity of Sm(III) and Tb(III) complexes with 2-aminobenzoic and 2-amino-5-chloro-benzoic acids

    Science.gov (United States)

    Essawy, Amr A.; Afifi, Manal A.; Moustafa, H.; El-Medani, S. M.

    2014-10-01

    The complexes of Sm(III) and Tb(III) with 2-aminobenzoic acid (anthranilic acid, AA) and 2-amino-5-chlorobenzoic acid (5-chloroanthranilic acid, AACl) were synthesized and characterized based on elemental analysis, IR and mass spectroscopy. The data are in accordance with 1:3 [Metal]:[Ligand] ratio. On the basis of the IR analysis, it was found that the metals were coordinated to bidentate anthranilic acid via the ionised oxygen of the carboxylate group and to the nitrogen of amino group. While in 5-chloroanthranilic acid, the metals were coordinated oxidatively to the bidentate carboxylate group without bonding to amino group; accordingly, a chlorine-affected coordination and reactivity-diversity was emphasized. Thermal analyses (TGA) and biological activity of the complexes were also investigated. Density Functional Theory (DFT) calculations at the B3LYP/6-311++G (d,p)_ level of theory have been carried out to investigate the equilibrium geometry of the ligand. The optimized geometry parameters of the complexes were evaluated using SDDALL basis set. Moreover, total energy, energy of HOMO and LUMO and Mullikan atomic charges were calculated. In addition, dipole moment and orientation have been performed and discussed.

  13. Isotropic and anisotropic nanocrystalline NdFeB bulk magnets prepared by binder-free high-velocity compaction technique

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Xiangxing [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Liu, Zhongwu, E-mail: zwliu@scut.edu.cn [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Yu, Hongya [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Xiao, Zhiyu [School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China); Zhang, Guoqing [Science and Technology on Advanced High Temperature Structural Materials Laboratory, Beijing Institute of Aeronautical Materials, Beijing 100095 (China)

    2015-09-15

    NdFeB powders were consolidated into nanocrystalline bulk magnets by a near-net-shape process of high-velocity compaction (HVC) at room temperature with no binder employed. The nanostructure can be maintained after compaction. The compacted magnets with relatively high density can inherit the coercivity of the starting powders. The mechanical strength of the HVCed magnet after heat treatment is comparable to that of the conventional bonded NdFeB magnets. The anisotropic magnet has also been prepared by hot deformation using HVCed magnet as the precursor. The remanence value along the pressing direction increased from 0.64 to 0.95 T and maximum energy product (BH){sub max} increased from 65 to 120 kJ/m{sup 3} after hot deformation. The processing–structure–properties relationships for both isotropic and anisotropic magnets are discussed. - Highlights: • HVC is a feasible binder-free approach for preparing NdFeB magnets. • The compacted magnets can inherit the coercivity of the starting powders. • The magnets post heat treatment have compression strength higher than bonded magnets. • The approach of HVC is a potential pre-process for anisotropic NdFeB bulk magnets.

  14. Isotropic and anisotropic nanocrystalline NdFeB bulk magnets prepared by binder-free high-velocity compaction technique

    International Nuclear Information System (INIS)

    Deng, Xiangxing; Liu, Zhongwu; Yu, Hongya; Xiao, Zhiyu; Zhang, Guoqing

    2015-01-01

    NdFeB powders were consolidated into nanocrystalline bulk magnets by a near-net-shape process of high-velocity compaction (HVC) at room temperature with no binder employed. The nanostructure can be maintained after compaction. The compacted magnets with relatively high density can inherit the coercivity of the starting powders. The mechanical strength of the HVCed magnet after heat treatment is comparable to that of the conventional bonded NdFeB magnets. The anisotropic magnet has also been prepared by hot deformation using HVCed magnet as the precursor. The remanence value along the pressing direction increased from 0.64 to 0.95 T and maximum energy product (BH) max increased from 65 to 120 kJ/m 3 after hot deformation. The processing–structure–properties relationships for both isotropic and anisotropic magnets are discussed. - Highlights: • HVC is a feasible binder-free approach for preparing NdFeB magnets. • The compacted magnets can inherit the coercivity of the starting powders. • The magnets post heat treatment have compression strength higher than bonded magnets. • The approach of HVC is a potential pre-process for anisotropic NdFeB bulk magnets

  15. DFT-Assisted Polymorph Identification from Lattice Raman Fingerprinting.

    Science.gov (United States)

    Bedoya-Martínez, Natalia; Schrode, Benedikt; Jones, Andrew O F; Salzillo, Tommaso; Ruzié, Christian; Demitri, Nicola; Geerts, Yves H; Venuti, Elisabetta; Della Valle, Raffaele Guido; Zojer, Egbert; Resel, Roland

    2017-08-03

    A combined experimental and theoretical approach, consisting of lattice phonon Raman spectroscopy and density functional theory (DFT) calculations, is proposed as a tool for lattice dynamics characterization and polymorph phase identification. To illustrate the reliability of the method, the lattice phonon Raman spectra of two polymorphs of the molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]benzothiophene are investigated. We show that DFT calculations of the lattice vibrations based on the known crystal structures, including many-body dispersion van der Waals (MBD-vdW) corrections, predict experimental data within an accuracy of ≪5 cm -1 (≪0.6 meV). Due to the high accuracy of the simulations, they can be used to unambiguously identify different polymorphs and to characterize the nature of the lattice vibrations and their relationship to the structural properties. More generally, this work implies that DFT-MBD-vdW is a promising method to describe also other physical properties that depend on lattice dynamics like charge transport.

  16. Complexes of DNA bases and Watson-Crick base pairs interaction with neutral silver Agn (n = 8, 10, 12) clusters: a DFT and TDDFT study.

    Science.gov (United States)

    Srivastava, Ruby

    2018-03-01

    We study the binding of the neutral Ag n (n = 8, 10, 12) to the DNA base-adenine (A), guanine (G) and Watson-Crick -adenine-thymine, guanine-cytosine pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential was used for silver and 6-31 + G ** was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Ag n -A,G/WC complexes were also studied using time-dependent density functional theory. The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Ag n -WC complexes. The vertical ionization potential, vertical electron affinity, hardness, and electrophilicity index of Ag n -DNA/WC complexes have also been discussed.

  17. Design methodology of single-feed compact near-isotropic antenna design

    KAUST Repository

    Su, Zhen

    2017-06-07

    The abundance of mobile wireless devices is giving rise to a new paradigm known as Internet of Things. In this paradigm, wireless devices will be everywhere and communicating with each other. Since they will be oriented randomly in the environment, they should be able to communicate equally in all directions in order to have stable communication link. Hence, compact near isotropic antennas are required, which can enable orientation insensitive communication. In this paper, we propose a simple design methodology to design a compact near-isotropic wire antenna based on equal vector potentials. As a proof of concept, a quarter wavelength monopole antennas has been designed that is wrapped on a 3D-printed box keeping the vector potentials in three orthogonal different directions equal. By optimizing the dimension of the antenna arms, a nearly isotropic radiation pattern is thus achieved. The results show that the antenna has a maximum gain of 2.2dBi at 900 MHz with gain derivation of 9.4dB.

  18. A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

    Science.gov (United States)

    Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

    2018-05-01

    The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

  19. Probing the reactivation process of sarin-inhibited acetylcholinesterase with α-nucleophiles: hydroxylamine anion is predicted to be a better antidote with DFT calculations.

    Science.gov (United States)

    Khan, Md Abdul Shafeeuulla; Lo, Rabindranath; Bandyopadhyay, Tusar; Ganguly, Bishwajit

    2011-08-01

    Inactivation of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat to human since AChE is a key enzyme in neurotransmission process. Oximes are used as potential reactivators of OP-inhibited AChE due to their α-effect nucleophilic reactivity. In search of more effective reactivating agents, model studies have shown that α-effect is not so important for dephosphylation reactions. We report the importance of α-effect of nucleophilic reactivity towards the reactivation of OP-inhibited AChE with hydroxylamine anion. We have demonstrated with DFT [B3LYP/6-311G(d,p)] calculations that the reactivation process of sarin-serine adduct 2 with hydroxylamine anion is more efficient than the other nucleophiles reported. The superiority of hydroxylamine anion to reactivate the sarin-inhibited AChE with sarin-serine adducts 3 and 4 compared to formoximate anion was observed in the presence and absence of hydrogen bonding interactions of Gly121 and Gly122. The calculated results show that the rates of reactivation process of adduct 4 with hydroxylamine anion are 261 and 223 times faster than the formoximate anion in the absence and presence of such hydrogen bonding interactions. The DFT calculated results shed light on the importance of the adjacent carbonyl group of Glu202 for the reactivation of sarin-serine adduct, in particular with formoximate anion. The reverse reactivation reaction between hydroxylamine anion and sarin-serine adduct was found to be higher in energy compared to the other nucleophiles, which suggests that this α-nucleophile can be a good antidote agent for the reactivation process. Copyright © 2011 Elsevier Inc. All rights reserved.

  20. Diels-Alder reactions for the rational design of benzo[b]thiophenes: DFT-based guidelines for synthetic chemists

    Science.gov (United States)

    Brasca, Romina; Kneeteman, María N.; Mancini, Pedro M. E.; Fabian, Walter M. F.

    2012-02-01

    In this work we studied the capability of several diene/dienophile pairs to undergo Diels-Alder (DA) reactions leading to benzo[b]thiophenes. A variety of synthetically and commercially available nitrothiophenes were chosen as dienophiles. Methyl 5-nitro-3-thiophenecarboxylate was selected as a potential strong electrophilic candidate based on some DFT-based properties and the substitution pattern of the expected product. The mechanistic details concerning the participation of this dienophile in polar DA reactions were investigated through a theoretical point of view. The results were compared with the experimental outcomes. This methodology should allow synthetic chemists to analyze DA reactions in detail in a stage prior to the synthetic job.