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Sample records for periodic dft calculations

  1. Treatment of delocalized electron transfer in periodic and embedded cluster DFT calculations: The case of Cu on ZnO (10(1)0).

    Science.gov (United States)

    Hellström, Matti; Spångberg, Daniel; Hermansson, Kersti

    2015-12-15

    We assess the consequences of the interface model-embedded-cluster or periodic-slab model-on the ability of DFT calculations to describe charge transfer (CT) in a particularly challenging case where periodic-slab calculations indicate a delocalized charge-transfer state. Our example is Cu atom adsorption on ZnO(10(1)0), and in fact the periodic slab calculations indicate three types of CT depending on the adsorption site: full CT, partial CT, and no CT. Interestingly, when full CT occurs in the periodic calculations, the calculated Cu atom adsorption energy depends on the underlying ZnO substrate supercell size, since when the electron enters the ZnO it delocalizes over as many atoms as possible. In the embedded-cluster calculations, the electron transferred to the ZnO delocalizes over the entire cluster region, and as a result the calculated Cu atom adsorption energy does not agree with the value obtained using a large periodic supercell, but instead to the adsorption energy obtained for a periodic supercell of roughly the same size as the embedded cluster. Different density functionals (of GGA and hybrid types) and basis sets (local atom-centered and plane-waves) were assessed, and we show that embedded clusters can be used to model Cu adsorption on ZnO(10(1)0), as long as care is taken to account for the effects of CT. © 2015 Wiley Periodicals, Inc.

  2. Synthesis, Spectroscopic Properties and DFT Calculation of Novel ...

    Indian Academy of Sciences (India)

    density functional theory (DFT) calculations. Keywords. ... time-dependent density functional theory (TD-DFT) calcu- lations. .... reaction, the pH of the solution was adjusted to 7 .... ORTEP diagram for L1 showing 30% probability ellipsoids.

  3. nmr spectroscopic study and dft calculations of vibrational analyses

    African Journals Online (AJOL)

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    2Plant, Drug and Scientific Research Centre, Anadolu University, 26470, ... Density functional theory (DFT) calculations provide excellent agreement with ..... simple correlation between 1JCH and the hybridization of the carbon atom involved; ...

  4. Muon contact hyperfine field in metals: A DFT calculation

    Science.gov (United States)

    Onuorah, Ifeanyi John; Bonfà, Pietro; De Renzi, Roberto

    2018-05-01

    In positive muon spin rotation and relaxation spectroscopy it is becoming customary to take advantage of density functional theory (DFT) based computational methods to aid the experimental data analysis. DFT-aided muon site determination is especially useful for measurements performed in magnetic materials, where large contact hyperfine interactions may arise. Here we present a systematic analysis of the accuracy of the ab initio estimation of muon's hyperfine contact field on elemental transition metals, performing state-of-the-art spin-polarized plane-wave DFT and using the projector-augmented pseudopotential approach, which allows one to include the core state effects due to the spin ordering. We further validate this method in not-so-simple, noncentrosymmetric metallic compounds, presently of topical interest for their spiral magnetic structure giving rise to skyrmion phases, such as MnSi and MnGe. The calculated hyperfine fields agree with experimental values in all cases, provided the spontaneous spin magnetization of the metal is well reproduced within the approach. To overcome the known limits of the conventional mean-field approximation of DFT on itinerant magnets, we adopt the so-called reduced Stoner theory [L. Ortenzi et al., Phys. Rev. B 86, 064437 (2012), 10.1103/PhysRevB.86.064437]. We establish the accuracy of the estimated muon contact field in metallic compounds with DFT and our results show improved agreement with experiments compared to those of earlier publications.

  5. 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.

  6. Advantages of GPU technology in DFT calculations of intercalated graphene

    Science.gov (United States)

    Pešić, J.; Gajić, R.

    2014-09-01

    Over the past few years, the expansion of general-purpose graphic-processing unit (GPGPU) technology has had a great impact on computational science. GPGPU is the utilization of a graphics-processing unit (GPU) to perform calculations in applications usually handled by the central processing unit (CPU). Use of GPGPUs as a way to increase computational power in the material sciences has significantly decreased computational costs in already highly demanding calculations. A level of the acceleration and parallelization depends on the problem itself. Some problems can benefit from GPU acceleration and parallelization, such as the finite-difference time-domain algorithm (FTDT) and density-functional theory (DFT), while others cannot take advantage of these modern technologies. A number of GPU-supported applications had emerged in the past several years (www.nvidia.com/object/gpu-applications.html). Quantum Espresso (QE) is reported as an integrated suite of open source computer codes for electronic-structure calculations and materials modeling at the nano-scale. It is based on DFT, the use of a plane-waves basis and a pseudopotential approach. Since the QE 5.0 version, it has been implemented as a plug-in component for standard QE packages that allows exploiting the capabilities of Nvidia GPU graphic cards (www.qe-forge.org/gf/proj). In this study, we have examined the impact of the usage of GPU acceleration and parallelization on the numerical performance of DFT calculations. Graphene has been attracting attention worldwide and has already shown some remarkable properties. We have studied an intercalated graphene, using the QE package PHonon, which employs GPU. The term ‘intercalation’ refers to a process whereby foreign adatoms are inserted onto a graphene lattice. In addition, by intercalating different atoms between graphene layers, it is possible to tune their physical properties. Our experiments have shown there are benefits from using GPUs, and we reached an

  7. Advantages of GPU technology in DFT calculations of intercalated graphene

    International Nuclear Information System (INIS)

    Pešić, J; Gajić, R

    2014-01-01

    Over the past few years, the expansion of general-purpose graphic-processing unit (GPGPU) technology has had a great impact on computational science. GPGPU is the utilization of a graphics-processing unit (GPU) to perform calculations in applications usually handled by the central processing unit (CPU). Use of GPGPUs as a way to increase computational power in the material sciences has significantly decreased computational costs in already highly demanding calculations. A level of the acceleration and parallelization depends on the problem itself. Some problems can benefit from GPU acceleration and parallelization, such as the finite-difference time-domain algorithm (FTDT) and density-functional theory (DFT), while others cannot take advantage of these modern technologies. A number of GPU-supported applications had emerged in the past several years (www.nvidia.com/object/gpu-applications.html). Quantum Espresso (QE) is reported as an integrated suite of open source computer codes for electronic-structure calculations and materials modeling at the nano-scale. It is based on DFT, the use of a plane-waves basis and a pseudopotential approach. Since the QE 5.0 version, it has been implemented as a plug-in component for standard QE packages that allows exploiting the capabilities of Nvidia GPU graphic cards (www.qe-forge.org/gf/proj). In this study, we have examined the impact of the usage of GPU acceleration and parallelization on the numerical performance of DFT calculations. Graphene has been attracting attention worldwide and has already shown some remarkable properties. We have studied an intercalated graphene, using the QE package PHonon, which employs GPU. The term ‘intercalation’ refers to a process whereby foreign adatoms are inserted onto a graphene lattice. In addition, by intercalating different atoms between graphene layers, it is possible to tune their physical properties. Our experiments have shown there are benefits from using GPUs, and we reached an

  8. 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.

  9. Proton transfers in the Strecker reaction revealed by DFT calculations

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2014-08-01

    Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

  10. Proton affinities of anionic bases: Trends across the periodic table, structural effects, and DFT validation

    NARCIS (Netherlands)

    Swart, M.; Bickelhaupt, F.M.

    2006-01-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton

  11. Systematic pseudopotentials from reference eigenvalue sets for DFT calculations: Pseudopotential files

    Directory of Open Access Journals (Sweden)

    Pablo Rivero

    2015-06-01

    Full Text Available We present in this article a pseudopotential (PP database for DFT calculations in the context of the SIESTA code [1–3]. Comprehensive optimized PPs in two formats (psf files and input files for ATM program are provided for 20 chemical elements for LDA and GGA exchange-correlation potentials. Our data represents a validated database of PPs for SIESTA DFT calculations. Extensive transferability tests guarantee the usefulness of these PPs.

  12. DFT and TD-DFT calculations of metallotetraphenylporphyrin and metallotetraphenylporphyrin fullerene complexes as potential dye sensitizers for solar cells

    Science.gov (United States)

    El Mahdy, A. M.; Halim, Shimaa Abdel; Taha, H. O.

    2018-05-01

    Density functional theory (DFT) and time-dependent DFT calculations have been employed to model metallotetraphenylporphyrin dyes and metallotetraphenylporphyrin -fullerene complexes in order to investigate the geometries, electronic structures, the density of states, non-linear optical properties (NLO), IR-vis spectra, molecular electrostatic potential contours, and electrophilicity. To calculate the excited states of the tetraphenyl porphyrin analogs, time-dependent density functional theory (TD-DFT) are used. Their UV-vis spectra were also obtained and a comparison with available experimental and theoretical results is included. The results reveal that the metal and the tertiary butyl groups of the dyes are electron donors, and the tetraphenylporphyrin rings are electron acceptors. The HOMOs of the dyes fall within the (TiO2)60 and Ti38O76 band gaps and support the issue of typical interfacial electron transfer reaction. The resulting potential drop of Mn-TPP-C60 increased by ca. 3.50% under the effect of the tertiary butyl groups. The increase in the potential drop indicates that the tertiary butyl complexes could be a better choice for the strong operation of the molecular rectifiers. The introduction of metal atom and tertiary butyl groups to the tetraphenyl porphyrin moiety leads to a stronger response to the external electric field and induces higher photo-to-current conversion efficiency. This also shifts the absorption in the dyes and makes them potential candidates for harvesting light in the entire visible and near IR region for photovoltaic applications.

  13. All-optical generation of DFT-S-OFDM superchannels using periodic sinc pulses.

    Science.gov (United States)

    Lowery, Arthur James; Zhu, Chen; Viterbo, Emanuele; Corcoran, Bill

    2014-11-03

    Discrete-Fourier-transform spread (DFT-S) optical Orthogonal Frequency Division Multiplexed (OFDM) signals offer improved nonlinearity performance in long haul optical communications systems, and can be used to form superchannels. In this paper we propose how DFT-S-OFDM superchannels can be generated and demultiplexed using all-optical techniques, and demonstrate the feasibility using numerical simulations. We also discuss how each wavelength channel is similar to recently proposed Orthogonally Time-Division Multiplexed (OrthTDM) systems using periodic-sinc pulses from, for example, a Nyquist laser. The key difference between OrthTDM and DFT-S-OFDM is the synchronization of the symbol boundaries of every modulation tributary; because of this we show that OrthTDM cannot be formed into superchannels that can be demultiplexed without penalties, but DFT-S-OFDM can be.

  14. Chemical Information revealed by Mössbauer spectroscopy and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Satoru, E-mail: snaka@hiroshima-u.ac.jp [Hiroshima University, Natural Science Center for Basic Research and Development (Japan)

    2017-11-15

    Mixed-valence state of binuclear metallocene derivatives and spin-crossover (SCO) phenomena of the assembled Fe(II) complexes have been studied by using Mössbauer spectroscopy. The understanding of the results obtained by Mössbauer spectra is well supported by means of X-ray structural analysis and density functional theory (DFT) calculation. Benchmark study of relativisitic DFT calculation by using Mössbauer isomer shifts of Eu, Np complexes reveals the validity of the calculation. Such study sheds light on the bonding character of 4f and 5f electron. These results are reviewed.

  15. Electronic annealing Fermi operator expansion for DFT calculations on metallic systems

    Science.gov (United States)

    Aarons, Jolyon; Skylaris, Chris-Kriton

    2018-02-01

    Density Functional Theory (DFT) calculations with computational effort which increases linearly with the number of atoms (linear-scaling DFT) have been successfully developed for insulators, taking advantage of the exponential decay of the one-particle density matrix. For metallic systems, the density matrix is also expected to decay exponentially at finite electronic temperature and linear-scaling DFT methods should be possible by taking advantage of this decay. Here we present a method for DFT calculations at finite electronic temperature for metallic systems which is effectively linear-scaling (O(N)). Our method generates the elements of the one-particle density matrix and also finds the required chemical potential and electronic entropy using polynomial expansions. A fixed expansion length is always employed to generate the density matrix, without any loss in accuracy by the application of a high electronic temperature followed by successive steps of temperature reduction until the desired (low) temperature density matrix is obtained. We have implemented this method in the ONETEP linear-scaling (for insulators) DFT code which employs local orbitals that are optimised in situ. By making use of the sparse matrix machinery of ONETEP, our method exploits the sparsity of Hamiltonian and density matrices to perform calculations on metallic systems with computational cost that increases asymptotically linearly with the number of atoms. We demonstrate the linear-scaling computational cost of our method with calculation times on palladium nanoparticles with up to ˜13 000 atoms.

  16. Structural characterization of Am(III) formate complexes. Combining EXAFS spectroscopy with DFT and thermodynamical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Rossberg, Andre [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures; Froehlich, D.R. [Heidelberg Univ. (Germany). Physikalisch-Chemisches Inst.

    2017-06-01

    We used iterative transformation factor analysis (ITFA) in order to isolate the EXAFS spectral contributions of the complexing ligand from a Am(III)/formate pH-series. Thermodynamic calculations were used as constraint for ITFA and for density functional theory (DFT) calculations to identify the coordination mode within the formed complexes.

  17. Calculation on uranium carbon oxygen system molecular structure by DFT

    International Nuclear Information System (INIS)

    Zhang Guangfeng; Wang Xiaolin; Zou Lexi; Sun Ying; Xue Weidong; Zhu Zhenghe; Wang Hongyan

    2001-01-01

    The authors study on the possible molecular structures U-C-O, U-O-C, C-U-O (angular structure C a nd linear structure C ∞υ ) of carbon monoxide interacting on uranium metal surface by Density functional theory (DFT). The uranium atom is used RECP (Relativistic Effective Core Potential) and contracted valence basis sets (6s5p2d4f)/[3s3p2d2f], and for carbon and oxygen atoms all are 6-311G basis sets. The author presents the results of energy optimum which shows that triple and quintuple state are more stable. The authors get the electronic state, geometry structure, energy, harmonic frequency, mechanical property, etc. of these twelve triple and quintuple state relative stable structures. The normal vibrational analytical figure of angular structure (C s ) and linear structure (C ∞υ ) is given at the same time. It is indicated that angular structure has lower energy than linear structure, moreover the angular structure of U-C-O( 3 A ) has the lowest energy. The bond strength between uranium atom and carbon monoxide is weak and between uranium atom and oxygen atom is slightly stronger than between uranium atom and carbon atom which the authors can know by superposition population and bond energy analysis among atoms

  18. Benchmarking the DFT+U method for thermochemical calculations of uranium molecular compounds and solids.

    Science.gov (United States)

    Beridze, George; Kowalski, Piotr M

    2014-12-18

    Ability to perform a feasible and reliable computation of thermochemical properties of chemically complex actinide-bearing materials would be of great importance for nuclear engineering. Unfortunately, density functional theory (DFT), which on many instances is the only affordable ab initio method, often fails for actinides. Among various shortcomings, it leads to the wrong estimate of enthalpies of reactions between actinide-bearing compounds, putting the applicability of the DFT approach to the modeling of thermochemical properties of actinide-bearing materials into question. Here we test the performance of DFT+U method--a computationally affordable extension of DFT that explicitly accounts for the correlations between f-electrons - for prediction of the thermochemical properties of simple uranium-bearing molecular compounds and solids. We demonstrate that the DFT+U approach significantly improves the description of reaction enthalpies for the uranium-bearing gas-phase molecular compounds and solids and the deviations from the experimental values are comparable to those obtained with much more computationally demanding methods. Good results are obtained with the Hubbard U parameter values derived using the linear response method of Cococcioni and de Gironcoli. We found that the value of Coulomb on-site repulsion, represented by the Hubbard U parameter, strongly depends on the oxidation state of uranium atom. Last, but not least, we demonstrate that the thermochemistry data can be successfully used to estimate the value of the Hubbard U parameter needed for DFT+U calculations.

  19. Spectroscopic and DFT studies of calix[4]arene: time-dependent DFT calculations for elucidating the variation in the excitation energies with geometry

    Energy Technology Data Exchange (ETDEWEB)

    Boo, Bong Hyun; Kwak, Hae Ran; Hong, Seung Ki [Chungnam National University, Daejeon (Korea, Republic of); Park, Chan Jo [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); No, Kwang Hyun [Sookmyung Womens University, Seoul (Korea, Republic of)

    2010-08-15

    We have searched low-lying conformers of calix[4]arene and found one global minimum having a cone shape, together with three conformers such as partial cone-shape conformers. We then elucidated the thermodynamics for the conformational changes by performing density-functional theory (DFT) calculations. The time-dependent DFT calculation enabled us to assign the absorption spectrum and to reveal a variation of the excitation energies with geometry.

  20. nmr spectroscopic study and dft calculations of giao nmr shieldings

    African Journals Online (AJOL)

    Preferred Customer

    3Department of Physics, Arts and Science Faculty, Dumlupinar University, Kütahya, ... 1H, 13C NMR chemical shifts and 1JCH coupling constants of .... then estimated using the corresponding TMS shieldings calculated in advance at the same.

  1. Synthesis, Spectroscopic Properties and DFT Calculation of Novel ...

    Indian Academy of Sciences (India)

    L1) identifies its molecular structure and reveals π-π stacking. The synthetic mechanisms for L2, L3 were studied by density functional theory calculations. And a comprehensive study of spectroscopic properties involving experimental data and ...

  2. Determination of intermolecular transfer integrals from DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Baumeier, Bjoern; Andrienko, Denis [Max-Planck Institute for Polymer Research, Mainz (Germany)

    2010-07-01

    Theoretical studies of charge transport in organic conducting systems pose a unique challenge since they require multiscale schemes that combine quantum-chemical, molecular dynamics and kinetic Monte-Carlo calculations. The description of the mobility of electrons and holes in the hopping regime relies on the determination of intermolecular hopping rates in large scale morphologies. Using Marcus theory these rates can be calculated from intermolecular transfer integrals and on-site energies. Here we present a detailed computational study on the accuracy and efficiency of density-functional theory based approaches to the determination of intermolecular transfer integrals. First, it is demonstrated how these can be obtained from quantum-chemistry calculations by forming the expectation value of a dimer Fock operator with frontier orbitals of two neighboring monomers based on a projective approach. We then consider the prototypical example of one pair out of a larger morphology of Tris(8-hydroxyquinolinato)aluminium (Alq3) and study the influence of computational parameters, e.g. the choice of basis sets, exchange-correlation functional, and convergence criteria, on the calculated transfer integrals. The respective accuracies and efficiencies are compared in order to derive an optimal strategy for future simulations based on the full morphology.

  3. Metal-mediated deamination of cytosine: experiment and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Šponer, Judit E.; Sanz Miguel, P. J.; Rodríguez-Santiago, L.; Erxleben, A.; Krumm, M.; Sodupe, M.; Šponer, Jiří; Lippert, B.

    2004-01-01

    Roč. 43, č. 40 (2004), s. 5396-5399 ISSN 1433-7851 R&D Projects: GA MŠk LN00A016 Institutional research plan: CEZ:AV0Z5004920 Keywords : cytosine * deamination * density functional calculations Subject RIV: BO - Biophysics Impact factor: 9.161, year: 2004

  4. Quantum-mechanical DFT calculation supported Raman spectroscopic study of some amino acids in bovine insulin.

    Science.gov (United States)

    Tah, Bidisha; Pal, Prabir; Roy, Sourav; Dutta, Debodyuti; Mishra, Sabyashachi; Ghosh, Manash; Talapatra, G B

    2014-08-14

    In this article Quantum mechanical (QM) calculations by Density Functional Theory (DFT) have been performed of all amino acids present in bovine insulin. Simulated Raman spectra of those amino acids are compared with their experimental spectra and the major bands are assigned. The results are in good agreement with experiment. We have also verified the DFT results with Quantum mechanical molecular mechanics (QM/MM) results for some amino acids. QM/MM results are very similar with the DFT results. Although the theoretical calculation of individual amino acids are feasible, but the calculated Raman spectrum of whole protein molecule is difficult or even quite impossible task, since it relies on lengthy and costly quantum-chemical computation. However, we have tried to simulate the Raman spectrum of whole protein by adding the proportionate contribution of the Raman spectra of each amino acid present in this protein. In DFT calculations, only the contributions of disulphide bonds between cysteines are included but the contribution of the peptide and hydrogen bonds have not been considered. We have recorded the Raman spectra of bovine insulin using micro-Raman set up. The experimental spectrum is found to be very similar with the resultant simulated Raman spectrum with some exceptions. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Structures of cefradine dihydrate and cefaclor dihydrate from DFT-D calculations

    DEFF Research Database (Denmark)

    van de Streek, Jacco; Rantanen, Jukka; Bond, Andrew D

    2013-01-01

    in the zwitterionic form in the two dihydrate structures. A potential ambiguity concerning the orientation of the cyclohexadienyl ring in cefradine dihydrate is also clarified, and on the basis of the calculated energies it is shown that disorder should not be expected at room temperature. The DFT-D methods can...

  6. Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

    Czech Academy of Sciences Publication Activity Database

    Socha, Ondřej; Hodgkinson, P.; Widdifield, C. M.; Yates, J. R.; Dračínský, Martin

    2017-01-01

    Roč. 121, č. 21 (2017), s. 4103-4113 ISSN 1089-5639 R&D Projects: GA ČR GA15-11223S Institutional support: RVO:61388963 Keywords : NMR spectroscopy * DFT calculations * quadrupolar coupling Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.847, year: 2016

  7. 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

  8. The Dirac equation in electronic structure calculations: Accurate evaluation of DFT predictions for actinides

    International Nuclear Information System (INIS)

    Wills, John M.; Mattsson, Ann E.

    2012-01-01

    Brooks, Johansson, and Skriver, using the LMTO-ASA method and considerable insight, were able to explain many of the ground state properties of the actinides. In the many years since this work was done, electronic structure calculations of increasing sophistication have been applied to actinide elements and compounds, attempting to quantify the applicability of DFT to actinides and actinide compounds and to try to incorporate other methodologies (i.e. DMFT) into DFT calculations. Through these calculations, the limits of both available density functionals and ad hoc methodologies are starting to become clear. However, it has also become clear that approximations used to incorporate relativity are not adequate to provide rigorous tests of the underlying equations of DFT, not to mention ad hoc additions. In this talk, we describe the result of full-potential LMTO calculations for the elemental actinides, comparing results obtained with a full Dirac basis with those obtained from scalar-relativistic bases, with and without variational spin-orbit. This comparison shows that the scalar relativistic treatment of actinides does not have sufficient accuracy to provide a rigorous test of theory and that variational spin-orbit introduces uncontrolled errors in the results of electronic structure calculations on actinide elements.

  9. Proton affinities of maingroup-element hydrides and noble gases: trends across the periodic table, structural effects, and DFT validation

    NARCIS (Netherlands)

    Swart, M.; Rosler, E.; Bickelhaupt, F.M.

    2006-01-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal neutral bases across the periodic system using the generalized gradient approximation (GGA) of the density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing

  10. Thermodynamic study of complexation of thorium with pyridine monocarboxylates by calorimetry and DFT calculations

    International Nuclear Information System (INIS)

    Rama Mohana Rao, D.; Rawat, Neetika; Sawant, R.M.; Tomar, B.S.; Manna, D.; Ghanty, T.K.

    2013-01-01

    Stability constants of Th(IV) complexes with pyridine mono-carboxylates, namely, picolinate, nicotinate and isonicotinate have been determined following potentiometric titration of the metal ion and ligand mixtures with NaOH solution of known concentration. These data were used during the analysis of the calorimetric titration data to obtain the enthalpy of complexation reactions. The experimental data have been compared with that obtained from the DFT based theoretical calculations. (author)

  11. Accurate structures and energetics of neutral-framework zeotypes from dispersion-corrected DFT calculations

    Science.gov (United States)

    Fischer, Michael; Angel, Ross J.

    2017-05-01

    Density-functional theory (DFT) calculations incorporating a pairwise dispersion correction were employed to optimize the structures of various neutral-framework compounds with zeolite topologies. The calculations used the PBE functional for solids (PBEsol) in combination with two different dispersion correction schemes, the D2 correction devised by Grimme and the TS correction of Tkatchenko and Scheffler. In the first part of the study, a benchmarking of the DFT-optimized structures against experimental crystal structure data was carried out, considering a total of 14 structures (8 all-silica zeolites, 4 aluminophosphate zeotypes, and 2 dense phases). Both PBEsol-D2 and PBEsol-TS showed an excellent performance, improving significantly over the best-performing approach identified in a previous study (PBE-TS). The temperature dependence of lattice parameters and bond lengths was assessed for those zeotypes where the available experimental data permitted such an analysis. In most instances, the agreement between DFT and experiment improved when the experimental data were corrected for the effects of thermal motion and when low-temperature structure data rather than room-temperature structure data were used as a reference. In the second part, a benchmarking against experimental enthalpies of transition (with respect to α-quartz) was carried out for 16 all-silica zeolites. Excellent agreement was obtained with the PBEsol-D2 functional, with the overall error being in the same range as the experimental uncertainty. Altogether, PBEsol-D2 can be recommended as a computationally efficient DFT approach that simultaneously delivers accurate structures and energetics of neutral-framework zeotypes.

  12. DFT LCAO and plane wave calculations of SrZrO3

    International Nuclear Information System (INIS)

    Evarestov, R.A.; Bandura, A.V.; Alexandrov, V.E.; Kotomin, E.A.

    2005-01-01

    The results of the density functional (DFT) LCAO and plane wave (PW) calculations of the electronic and structural properties of four known SrZrO 3 phases (Pm3m, I4/mcm, Cmcm and Pbnm) are presented and discussed. The calculated unit cell energies and relative stability of these phases agree well with the experimental sequence of SrZrO 3 phases as the temperature increases. The lattice structure parameters optimized in the PW calculations for all four phases are in good agreement with the experimental neutron diffraction data. The LCAO and PW results for the electronic structure, density of states and chemical bonding in the cubic phase (Pm3m) are discussed in detail and compared with the results of previous PW calculations. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. DFT LCAO and plane wave calculations of SrZrO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Evarestov, R.A.; Bandura, A.V.; Alexandrov, V.E. [Department of Quantum Chemistry, St. Petersburg State University, 26 Universitetskiy Prospekt, Stary Peterhof 198504 (Russian Federation); Kotomin, E.A. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstr. 1, 70569, Stuttgart (Germany)

    2005-02-01

    The results of the density functional (DFT) LCAO and plane wave (PW) calculations of the electronic and structural properties of four known SrZrO{sub 3} phases (Pm3m, I4/mcm, Cmcm and Pbnm) are presented and discussed. The calculated unit cell energies and relative stability of these phases agree well with the experimental sequence of SrZrO{sub 3} phases as the temperature increases. The lattice structure parameters optimized in the PW calculations for all four phases are in good agreement with the experimental neutron diffraction data. The LCAO and PW results for the electronic structure, density of states and chemical bonding in the cubic phase (Pm3m) are discussed in detail and compared with the results of previous PW calculations. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Internal dynamics in helical molecules studied by X-ray diffraction, NMR spectroscopy and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Storch, Jan; Církva, Vladimír; Císařová, I.; Sýkora, Jan

    2017-01-01

    Roč. 19, č. 4 (2017), s. 2900-2907 ISSN 1463-9076 R&D Projects: GA ČR GA15-11223S; GA ČR GA15-12719S Institutional support: RVO:61388963 ; RVO:67985858 Keywords : helicene * NMR spectroscopy * DFT calculations Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry; Physical chemistry (UCHP-M) Impact factor: 4.123, year: 2016 http://pubs.rsc.org/en/content/articlehtml/2013/cp/c6cp07552e

  15. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert

    2014-05-25

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  16. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert; Correa, Andrea; Pump, Eva; Cavallo, Luigi

    2014-01-01

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  17. Molecular structure and spectroscopic properties of 4-nitrocatechol at different pH: UV-visible, Raman, DFT and TD-DFT calculations

    International Nuclear Information System (INIS)

    Cornard, Jean-Paul; Rasmiwetti; Merlin, Jean-Claude

    2005-01-01

    We investigated theoretically, by density functional theoretical calculations and by vibrational and electronic spectroscopies, the structure and the molecular spectroscopic properties of the 4-nitrocatechol molecule with varying pH. The lower energy stable structures of the neutral, monoanion and dianion forms were compared, and influence of water solvation was examined. The Raman and UV-visible spectra of 4-nitrocatechol and of its singly deprotonated form were recorded by varying the pH from 2 to 9. A calculation of the vibrational frequencies has allowed a complete assignment of the Raman spectra of the two forms of 4-nitrocatechol, and has permitted to investigate the evolution of vibrational normal modes upon deprotonation. Based on the molecular orbital analysis and the time dependent DFT (TD-DFT) calculations, we discussed the electronic structure and the assignment of the absorption bands in the electronic spectra of 4-nitrocatechol and mono-deprotonated 4-nitrocatechol

  18. Conformational analysis of capsaicin using 13C, 15N MAS NMR, GIAO DFT and GA calculations

    Science.gov (United States)

    Siudem, Paweł; Paradowska, Katarzyna; Bukowicki, Jarosław

    2017-10-01

    Capsaicin produced by plants from genus Capsicum exerts multiple pharmacological effects and has found applications in food and pharmaceutical industry. The alkaloid was studied by a combined approach: solid-state NMR, GA conformational search and GIAO DFT methods. The 13C CPMAS NMR spectra were recorded using variable contact time and dipolar dephasing experiments. The results of cross-polarization (CP) kinetics, such as TCP values and long T1ρH (100-200 ms), indicated that the capsaicin molecule is fairly mobile, especially at the end of the aliphatic chain. The15N MAS NMR spectrum showed one narrow signal at -255 ppm. Genetic algorithm (GA) search with multi modal optimization was used to find low-energy conformations of capsaicin. Theoretical GIAO DFT calculations were performed using different basis sets to characterize five selected conformations. 13C CPMAS NMR was used as a validation method and the experimental chemical shifts were compared with those calculated for selected stable conformers. Conformational analysis suggests that the side chain can be bent or extended. A comparison of the experimental and the calculated chemical shifts indicates that solid capsaicin does not have the same structure as those established by PWXRD.

  19. 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.

  20. 6-Aminocoumarin-naphthoquinone conjugates: design, synthesis, photophysical and electrochemical properties and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Fabio S.; Ronconi, Celia M.; Sousa, Mikaelly O.B.; Silveira, Gleiciani Q.; Vargas, Maria D., E-mail: miranda@vm.uff.br, E-mail: mdvargascp@gmail.com [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Quimica

    2014-01-15

    Four novel 6-aminocoumarin-naphthoquinone conjugates were synthesized and their photophysical and electrochemical properties, investigated. 2-Chloro-3-(2-oxo-2H-chromen-6- ylamino)-1,4-naphthoquinone 1 did not present appreciable fluorescence in solution in comparison with 6-aminocoumarin, 6-AC. In order to understand the reasons for the fluorescence quenching in this compound, two strategies were attempted. Firstly, compound 1 was N-methylated to remove the intramolecular N-H...O=C electrostatic interaction that maintained the two units fixed, but the emission properties of the product 2 were not significantly different from those of 1. Time-dependent density functional theory (TD-DFT) calculations of compounds 1 and 2 indicate that the fluorescence quenching is related to the electron acceptor character of the naphthoquinone ring. The second strategy, therefore, involved the substitution of the chlorine atom in position 2 of the naphthoquinone nucleus for different electron donor groups (compounds 3-5), but again the emission properties did not change significantly. To explain these experimental findings, TD-DFT calculations of the ground (S{sub 0}) and excited (S{sub 1}) states of all molecules in solution were carried out. The results suggest that the energy states in these conjugates are such that the fluorescent group (6-AC) donates electrons to the naphthoquinone LUMO resulting in an oxidative photoinduced electron transfer (oxidative-PET). (author)

  1. SU-C-204-03: DFT Calculations of the Stability of DOTA-Based-Radiopharmaceuticals

    Energy Technology Data Exchange (ETDEWEB)

    Khabibullin, A.R.; Woods, L.M. [University of South Florida, Tampa, Florida (United States); Karolak, A.; Budzevich, M.M.; Martinez, M.V. [H. Lee Moffitt Cancer Center and Research Institute, Tampa, Florida (United States); McLaughlin, M.L.; Morse, D.L. [University of South Florida, Tampa, Florida (United States); H. Lee Moffitt Cancer Center and Research Institute, Tampa, Florida (United States)

    2016-06-15

    Purpose: Application of the density function theory (DFT) to investigate the structural stability of complexes applied in cancer therapy consisting of the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelated to Ac225, Fr221, At217, Bi213, and Gd68 radio-nuclei. Methods: The possibility to deliver a toxic payload directly to tumor cells is a highly desirable aim in targeted alpha particle therapy. The estimation of bond stability between radioactive atoms and the DOTA chelating agent is the key element in understanding the foundations of this delivery process. Thus, we adapted the Vienna Ab-initio Simulation Package (VASP) with the projector-augmented wave method and a plane-wave basis set in order to study the stability and electronic properties of DOTA ligand chelated to radioactive isotopes. In order to count for the relativistic effect of radioactive isotopes we included Spin-Orbit Coupling (SOC) in the DFT calculations. Five DOTA complex structures were represented as unit cells, each containing 58 atoms. The energy optimization was performed for all structures prior to calculations of electronic properties. Binding energies, electron localization functions as well as bond lengths between atoms were estimated. Results: Calculated binding energies for DOTA-radioactive atom systems were −17.792, −5.784, −8.872, −13.305, −18.467 eV for Ac, Fr, At, Bi and Gd complexes respectively. The displacements of isotopes in DOTA cages were estimated from the variations in bond lengths, which were within 2.32–3.75 angstroms. The detailed representation of chemical bonding in all complexes was obtained with the Electron Localization Function (ELF). Conclusion: DOTA-Gd, DOTA-Ac and DOTA-Bi were the most stable structures in the group. Inclusion of SOC had a significant role in the improvement of DFT calculation accuracy for heavy radioactive atoms. Our approach is found to be proper for the investigation of structures with DOTA

  2. 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.

  3. 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.

  4. 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.

  5. MCD spectroscopy and TD-DFT calculations of low symmetry subnaphthalocyanine analogs.

    Science.gov (United States)

    Mack, John; Otaki, Tatsuya; Durfee, William S; Kobayashi, Nagao; Stillman, Martin J

    2014-07-01

    Magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations are used to analyze the electronic structure and optical properties of low-symmetry subnaphthalocyanine analogs with AAB and ABB structures formed during mixed condensations of tetrafluorophthalonitrile and 2,3-naphthalenedicarbonitrile. The results demonstrate that trends observed in the properties of phthalocyanine analogs can be used to fine tune the optical properties so that the Q(0,0) bands lie in the red region, in a manner that does not significantly destabilize the highest occupied molecular orbital (HOMO) energy relative to that of the parent subphthalocyanine ligand. Attempts to study the spectroscopy of anion radical species proved unsuccessful, since they proved to be unstable. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Actinide-lanthanide separation by bipyridyl-based ligands. DFT calculations and experimental results

    International Nuclear Information System (INIS)

    Borisova, Nataliya E.; Eroshkina, Elizaveta A.; Korotkov, Leonid A.; Ustynyuk, Yuri A.; Alyapyshev, Mikhail Yu.; Eliseev, Ivan I.; Babain, Vasily A.

    2011-01-01

    In order to gain insights into effect of substituents on selectivity of Am/Eu separation, the synthesis and extractions tests were undertaken on the series of bipyridyl-based ligands (amides of 2,2'-bipyridyl-6,6'-dicarboxylic acid: L Ph - N,N'-diethyl-N,N'-diphenyl amide; L Bu2 - tetrabutyl amide; L Oct2 - tetraoctyl amide; L 3FPh - N,N'-diethyl-N,N'-bis-(3-fluorophenyl) amide; as well as N,N'-diethyl-N,N'-diphenyl amide of 4,4'-dibrom-2,2'-bipyridyl-6,6'-dicarboxylic acid and N,N'-diethyl-N,N'-diphenyl amide of 4,4'-dinitro-2,2'-bipyridyl-6,6'-dicarboxylic acid) as well as structure and stability of their complexes with lanthanides and actinides were studied. The extraction tests were performed for Am, lanthanide series and transition metals in polar diluents in presence of chlorinated cobalt dicarbolide and have shown high distribution coefficients for Am. Also was found that the type of substituents on amidic nitrogen exerts great influence on the extraction of light lanthanides. For understanding of the nature of this effect we made QC-calculations at DFT level, binding constants determination and X-Ray structure determination of the complexes. The UV/VIS titration performed show that the composition of all complexes of the amides with lanthanides in solution is 1:1. In spite of the binding constants are high (lgβ about 6-7 in acetonitrile solution), lanthanide ions have binding constants with the same order of magnitude for dialkyl substituted extractants. The X-Ray structures of the complexes of bipyridyl-based amides show the composition of 1:1 and the coordination number of the ions being 10. The DFT optimized structures of the compounds are in good agreement with that obtained by X-Ray. The gas phase affinity of the amides to lanthanides shows strong correlation with the distribution ratios. We can infer that the bipyridyl-based amides form complexes with metal nitrates which have similar structure in solid and gas phases and in solution, and the DFT

  7. Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

    Science.gov (United States)

    Ahmad, Saeed; Nadeem, Shafqat; Anwar, Aneela; Hameed, Abdul; Tirmizi, Syed Ahmed; Zierkiewicz, Wiktor; Abbas, Azhar; Isab, Anvarhusein A.; Alotaibi, Mshari A.

    2017-08-01

    Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N,N‧-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm-1 in IR and resonances around 120-130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN- carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol-1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol-1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

  8. FT-IR, FT-Raman spectra and DFT calculations of melaminium perchlorate monohydrate

    Science.gov (United States)

    Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

    2013-08-01

    Melaminium perchlorate monohydrate (MPM), an organic material has been synthesized by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MPM crystal belongs to triclinic system with space group P-1. FTIR and FT Raman spectra are recorded at room temperature. Functional group assignment has been made for the melaminium cations and perchlorate anions. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory (DFT) calculations using Firefly (PC GAMESS) version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with experimental values. The assignment of the bands has been made on the basis of the calculated PED. The Mulliken charges, HOMO-LUMO orbital energies are analyzed directly from Firefly program log files and graphically illustrated. HOMO-LUMO energy gap and other related molecular properties are also calculated. The theoretically constructed FT-IR and FT-Raman spectra of MPM coincide with the experimental one. The chemical structure of the compound has been established by 1H and 13C NMR spectra. No detectable signal was observed during powder test for second harmonic generation.

  9. 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.

  10. Electronic and optical properties of GaN under pressure: DFT calculations

    Science.gov (United States)

    Javaheri, Sahar; Boochani, Arash; Babaeipour, Manuchehr; Naderi, Sirvan

    2017-12-01

    Optical and electronic properties of ZB, RS and WZ structures of gallium nitride (GaN) are studied in equilibrium and under pressure using the first-principles calculation in the density functional theory (DFT) framework to obtain quantities like dielectric function, loss function, reflectance and absorption spectra, refractive index and their relation parameters. The electronic properties are studied using EV-GGA and GGA approximations and the results calculated by EV-GGA approximation were found to be much closer to the experimental results. The interband electron transitions are studied using the band structure and electron transition peaks in the imaginary part of the dielectric function; these transitions occur in three structures from N-2p orbital to Ga-4s and Ga-4p orbitals in the conduction band. Different optical properties of WZ structure were calculated in two polarization directions of (100) and (001) and the results were close to each other. Plasmon energy corresponding to the main peak of the energy-loss function in RS with the value of 26 eV was the highest one, which increased under pressure. In general, RS shows more different properties than WZ and ZB.

  11. 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.

  12. Atomic adsorption on graphene with a single vacancy: systematic DFT study through the periodic table of elements

    Science.gov (United States)

    Pašti, Igor A.; Jovanović, Aleksandar; Dobrota, Ana S.; Mentus, Slavko V.; Johansson, Börje; Skorodumova, Natalia V.

    Vacancies in graphene present sites of altered chemical reactivity and open possibilities to tune graphene properties by defect engineering. The understanding of chemical reactivity of such defects is essential for successful implementation of carbon materials in advanced technologies. We report the results of a systematic DFT study of atomic adsorption on graphene with a single vacancy for the elements of rows 1 to 6 of the Periodic Table of Elements (PTE), excluding lanthanides. The calculations have been performed using PBE, long-range dispersion interaction-corrected PBE (PBE+D2 and PBE+D3) and non-local vdW-DF2 functional. We find that most elements strongly bind to the vacancy, except for the elements of groups 11 and 12, and noble gases, for which the contribution of dispersion interaction to bonding is most significant. The strength of the interaction with the vacancy correlates with the cohesive energy of the elements in their stable phases: the higher the cohesive energy is the stronger bonding to the vacancy can be expected. As most atoms can be trapped at the SV site we have calculated the potentials of dissolution and found that in most cases the metals adsorbed at the vacancy are more "noble" than they are in their corresponding stable phases.

  13. Possible reaction pathways of the lincomycin molecule according to the DFT calculation method

    Directory of Open Access Journals (Sweden)

    Eren Bahar

    2017-01-01

    Full Text Available Human-used antibiotics are eliminated from the body with little or no transformation at all. Traces of eliminated antibiotics enter the receiving environment directly since they cannot be treated in prevalent wastewater treatment facilities. Thus, wastewaters containing traces of antibiotics have to be treated accordingly. Lincomycin is subsequently isolated from Streptomyces lincolnensis. Lincomycin and its derivatives are antibiotics exhibiting biological activity against Gram-positive bacteria, and are natural antibiotics in the environment as pollutants. This study aims to predict the degradation mechanism of lincomycin molecule in the gaseous phase and aqueous media. Probable reaction path of lincomycin molecule with OH radicals was analyzed. Optimized geometry was calculated via Gauss View 5. Subsequently, the lowest energy status was determined through geometric optimization via Gaussian 09 program. Aiming to determine the intermediates in photocatalytic degradation mechanism of lincomycin, geometric optimization of the molecule was realized through DFT method. Activation energy for the probable reaction path was calculated, and their most stable state from the thermodynamic perspective determined for the gaseous phase and aqueous media. Impact of water solvent was investigated using the conductor-like screening solvation model (COSMO. The predicted mechanism was confirmed by comparison with experimental results on simple structures reported in literature.

  14. Structural and Thermodynamic Analysis of the First Mononuclear Aqueous Aluminum Citrate Complex Using DFT Calculations.

    Science.gov (United States)

    de Noronha, Antonio Luiz Oliveira; Guimarães, Luciana; Duarte, Hélio Anderson

    2007-05-01

    Structural and thermodynamic properties of the mononuclear Al/citrate complexes have been theoretically investigated aiming to understand the coordination mechanism at an atomic level. GGA-DFT/PCM calculations have been performed for the different conformations and tautomers arising from the Al(3+) and citric acid (H3L) interaction in aqueous solution. The Gibbs reaction energies were estimated based on the reaction of the trigonal planar Al(OH)3 and H3L to form different Al-citrate complexes. The estimated Gibbs free reaction energies for the [AlL], [AlHL](+), and [Al(OH)L](-) species are in good agreement with the experimental values. In these species, the Al(3+) center is coordinated by two carboxylic and the tertiary hydroxyl groups of the citrate. Conversely to what has been proposed based on the experiments, the present theoretical calculations indicate that the citric acid hydroxyl group remains protonated upon the coordination of Al(3+). In fact, our model turns out to be more consistent with the relative pKa values of citrate protonation groups and with the hydrolysis constant of the H2O bound to Al(3+) leading to better agreement with the available experimental data.

  15. 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)

  16. Optimal Location of Vanadium in Muscovite and Its Geometrical and Electronic Properties by DFT Calculation

    Directory of Open Access Journals (Sweden)

    Qiushi Zheng

    2017-02-01

    Full Text Available Vanadium-bearing muscovite is the most valuable component of stone coal, which is a unique source of vanadium manufacture in China. Numbers of experimental studies have been carried out to destroy the carrier muscovite’s structure for efficient extraction of vanadium. Hence, the vanadium location is necessary for exploring the essence of vanadium extraction. Although most infer that vanadium may substitute for trivalent aluminium (Al as the isomorphism in muscovite for the similar atomic radius, there is not enough experimental evidence and theoretical supports to accurately locate the vanadium site in muscovite. In this study, the muscovite model and optimal location of vanadium were calculated by density functional theory (DFT. We find that the vanadium prefers to substitute for the hexa-coordinated aluminum of muscovite for less deformation and lower substitution energy. Furthermore, the local geometry and relative electronic properties were calculated in detail. The basal theoretical research of muscovite contained with vanadium are reported for the first time. It will make a further influence on the technology development of vanadium extraction from stone coal.

  17. Ammonia IRMS-TPD measurements and DFT calculation on acidic hydroxyl groups in CHA-type zeolites.

    Science.gov (United States)

    Suzuki, Katsuki; Sastre, German; Katada, Naonobu; Niwa, Miki

    2007-12-07

    Brønsted acidity of H-chabazite (CHA) zeolites (Si : Al(2) = 4.2) was investigated by means of ammonia infrared-mass spectrometry/temperature-programmed desorption (IRMS-TPD) methods and density functional calculations. Four IR bands were observed at 3644, 3616, 3575 and 3538 cm(-1), and they were ascribable to the acidic OH groups on four nonequivalent oxygen sites in the CHA structure. The absorption band at 3538 cm(-1) was attributed to the O(4)H in the 6-membered ring (MR), and ammonia adsorption energy (DeltaU) of this OH group was the lowest among the 4 kinds of OH groups. The other 3 bands were assigned to the acidic OH groups in 8MR. It was observed that the DeltaU in 8 and 6MR were 131 (+/-3) and 101 kJ mol(-1), respectively. On the other hand, the density functional theory (DFT) calculations within periodic boundary conditions yielded the adsorption energies on these OH groups in 8 and 6MR to be ca. 130 and 110 kJ mol(-1), respectively, in good agreement with the experimentally-observed values.

  18. DFT calculations on spectroscopic and structural properties of a NLO chromophore

    Science.gov (United States)

    Altürk, Sümeyye; Avci, Davut; Tamer, Ömer; Atalay, Yusuf

    2016-03-01

    The molecular geometry optimization, vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of 2-(1'-(4'''-Methoxyphenyl)-5'-(thien-2″-yl)pyrrol-2'-yl)-1,3-benzothiazole as potential nonlinear optical (NLO) material were calculated using density functional theory (DFT) HSEh1PBE method with 6-311G(d,p) basis set. The best of our knowledge, this study have not been reported to date. Additionally, a detailed vibrational study was performed on the basis of potential energy distribution (PED) using VEDA program. It is noteworthy that NMR chemical shifts are quite useful for understanding the relationship between the molecular structure and electronic properties of molecules. The computed IR and NMR spectra were used to determine the types of the experimental bands observed. Predicted values of structural and spectroscopic parameters of the chromophore were compared with each other so as to display the effects of the different substituents on the spectroscopic and structural properties. Obtained data showed that there is an agreement between the predicted and experimental data.

  19. Design of Pd-Based Bimetallic Catalysts for ORR: A DFT Calculation Study

    Directory of Open Access Journals (Sweden)

    Lihui Ou

    2015-01-01

    Full Text Available Developing Pd-lean catalysts for oxygen reduction reaction (ORR is the key for large-scale application of proton exchange membrane fuel cells (PEMFCs. In the present paper, we have proposed a multiple-descriptor strategy for designing efficient and durable ORR Pd-based alloy catalysts. We demonstrated that an ideal Pd-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pd, and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pd-M alloys, Pd-V, Pd-Fe, Pd-Zn, Pd-Nb, and Pd-Ta, are identified theoretically to have stable Pd segregated surface and improved ORR activity. Factors affecting these properties are analyzed. The alloy formation energy of Pd with transition metals M can be mainly determined by their electron interaction. This may be the origin of the negative alloy formation energy for Pd-M alloys. The surface segregation energy of Pd is primarily determined by the surface energy and the atomic radius of M. The metals M which have smaller atomic radius and higher surface energy would tend to favor the surface segregation of Pd in corresponding Pd-M alloys.

  20. Indium local geometry in In-Sb-Te thin films using XANES and DFT calculations

    Science.gov (United States)

    Bilovol, V.; Gil Rebaza, A. V.; Mudarra Navarro, A. M.; Errico, L.; Fontana, M.; Arcondo, B.

    2017-12-01

    In-Sb-Te when is a thin film presents a huge difference in its electrical resistivity when transform from the amorphous (insulating) to the crystalline (conducting) phase. This property made this system one of the main phase-change materials used in the data storage industry. The change in the electrical conductivity is probably associated to a change in the bonding geometry of some of its constituents. To explore this point, we present in this work an study of the bonding geometry of In atoms in In-Sb-Te films by means of In K-edge X-ray absorption near edge structure (XANES) spectroscopy using synchrotron radiation in both as deposited (amorphous) and crystalline thin films obtained as a result of resistance (R) vs temperature (T) measurements. Comparison of the XANES spectra obtained for ternary amorphous films and binary crystalline reference films suggests that in amorphous films the bonding geometry of In atoms is tetrahedral-like. After the thermal annealing has been carried out the differences in the XANES spectra of the as deposited and the annealed films indicate that the bonding geometry of In atoms changes. Based on X-ray diffraction results and ab initio calculations in the framework of the Density Functional Theory (DFT) we show that the new coordination geometry is associated with a tendency of In atoms towards octahedral-like.

  1. 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...

  2. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Chavda, Bhavin R., E-mail: chavdabhavin9@gmail.com; Dubey, Rahul P.; Patel, Urmila H. [Department of Physics, Sardar Patel University, Vallabh Vidyanagar-388120, Gujarat (India); Gandhi, Sahaj A. [Bhavan’s Shri I.L. Pandya Arts-Science and Smt. J.M. shah Commerce College, Dakar, Anand -388001, Gujarat, Indian (India); Barot, Vijay M. [P. G. Center in Chemistry, Smt. S. M. Panchal Science College, Talod, Gujarat 383 215 (India)

    2016-05-06

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb –London –Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  3. Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

    Science.gov (United States)

    Fischer, Michael; Bell, Robert G

    2014-10-21

    The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount

  4. Surface study of gallium- and aluminum- doped graphenes upon adsorption of cytosine: DFT calculations

    International Nuclear Information System (INIS)

    Shokuhi Rad, Ali; Zareyee, Daryoush; Peyravi, Majid; Jahanshahi, Mohsen

    2016-01-01

    Highlights: • P1 and P4 are the most stable adsorption configurations for cytosine. • NBO analysis show n-type semiconductor property for both Al- and Ga-doped graphenes. • Important changes in the HOMO and LUMO of doped graphene upon adsorption of cytosine. • Increase in the conductivity of system when cytosine is adsorbed on doped graphenes. - Abstract: The adsorption of cytosine molecule on Al- and Ga- doped graphenes is studied using first-principles density functional theory (DFT) calculations. The energetically most stable geometries of cytosine on both Al- and Ga- doped graphenes are determined and the adsorption energies are calculated. The net charge of transfer as well as local charge of doped atoms upon adsorption of cytosine are studied by natural bond orbitals (NBO) analysis. Orbital hybridizing of complexes was searched by frontier molecular orbital theory (FMO), and density of states (DOS). Depending on the side of cytosine, there are four possible sites for its adsorption on doped graphene; denoted as P1, P2, P3, and P4, respectively. The order of binding energy in the case of Al-doped graphene is found as P1 > P4 > P3 > P2. Interestingly, the order in the case of Ga-doped graphene changes to: P4 ∼ P1 > P3 > P2. Both surfaces show superior adsorbent property, resulting chemisorption of cytosine, especially at P1 and P4 position configurations. The NBO charge analysis reveals that the charge transfers from Al- and Ga- doped graphene sheets to cytosine. The electronic properties of both surfaces undertake important changes after cytosine adsorption, which indicates notable change in its electrical conductivity.

  5. Surface study of gallium- and aluminum- doped graphenes upon adsorption of cytosine: DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Shokuhi Rad, Ali, E-mail: a.shokuhi@gmail.com [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Zareyee, Daryoush [Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Peyravi, Majid; Jahanshahi, Mohsen [Faculty of Chemical Engineering, Babol University of Technology, Babol (Iran, Islamic Republic of)

    2016-12-30

    Highlights: • P1 and P4 are the most stable adsorption configurations for cytosine. • NBO analysis show n-type semiconductor property for both Al- and Ga-doped graphenes. • Important changes in the HOMO and LUMO of doped graphene upon adsorption of cytosine. • Increase in the conductivity of system when cytosine is adsorbed on doped graphenes. - Abstract: The adsorption of cytosine molecule on Al- and Ga- doped graphenes is studied using first-principles density functional theory (DFT) calculations. The energetically most stable geometries of cytosine on both Al- and Ga- doped graphenes are determined and the adsorption energies are calculated. The net charge of transfer as well as local charge of doped atoms upon adsorption of cytosine are studied by natural bond orbitals (NBO) analysis. Orbital hybridizing of complexes was searched by frontier molecular orbital theory (FMO), and density of states (DOS). Depending on the side of cytosine, there are four possible sites for its adsorption on doped graphene; denoted as P1, P2, P3, and P4, respectively. The order of binding energy in the case of Al-doped graphene is found as P1 > P4 > P3 > P2. Interestingly, the order in the case of Ga-doped graphene changes to: P4 ∼ P1 > P3 > P2. Both surfaces show superior adsorbent property, resulting chemisorption of cytosine, especially at P1 and P4 position configurations. The NBO charge analysis reveals that the charge transfers from Al- and Ga- doped graphene sheets to cytosine. The electronic properties of both surfaces undertake important changes after cytosine adsorption, which indicates notable change in its electrical conductivity.

  6. Electronic structure of O-doped SiGe calculated by DFT + U method

    Science.gov (United States)

    Zhao, Zong-Yan; Yang, Wen; Yang, Pei-Zhi

    2016-12-01

    To more in depth understand the doping effects of oxygen on SiGe alloys, both the micro-structure and properties of O-doped SiGe (including: bulk, (001) surface, and (110) surface) are calculated by DFT + U method in the present work. The calculated results are as follows. (i) The (110) surface is the main exposing surface of SiGe, in which O impurity prefers to occupy the surface vacancy sites. (ii) For O interstitial doping on SiGe (110) surface, the existences of energy states caused by O doping in the band gap not only enhance the infrared light absorption, but also improve the behaviors of photo-generated carriers. (iii) The finding about decreased surface work function of O-doped SiGe (110) surface can confirm previous experimental observations. (iv) In all cases, O doing mainly induces the electronic structures near the band gap to vary, but is not directly involved in these variations. Therefore, these findings in the present work not only can provide further explanation and analysis for the corresponding underlying mechanism for some of the experimental findings reported in the literature, but also conduce to the development of μc-SiGe-based solar cells in the future. Project supported by the Natural Science Foundation of Yunnan Province, China (Grant No. 2015FB123), the 18th Yunnan Province Young Academic and Technical Leaders Reserve Talent Project, China (Grant No. 2015HB015), and the National Natural Science Foundation of China (Grant No. U1037604).

  7. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xinye [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Huang, Yaji, E-mail: heyyj@seu.edu.cn [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Pan, Zhigang [College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009 (China); Wang, Yongxing; Liu, Changqi [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China)

    2015-09-15

    Highlights: • Al surface after dehydroxylation is active while Si surface is inert. • The active sites are the unsaturated Al atoms and O atoms losing H atom. • PbO is the most suitable species for adsorption. • Increasing the activities of Al atoms can enhance the performance of kaolinite. • Produce of amorphous silica is a potential path to enhance the performance of kaolinite. - Abstract: Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl{sub 2} molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl{sub 2}. Considering the energy barriers, it is easy for PbO and PbCl{sub 2} to adsorb on Al surfaces but difficult to escape. The high energy barriers of de–HCl process cause the difficulties of PbCl{sub 2} to form PbO·Al{sub 2}O{sub 3}·2SiO{sub 2} with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent.

  8. 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.

  9. A systematic theoretical study of the electronic structures of porphyrin dimers: DFT and TD-DFT calculations on diporphyrins linked by ethane, ethene, ethyne, imine, and azo bridges.

    Science.gov (United States)

    Rintoul, Llew; Harper, Shannon R; Arnold, Dennis P

    2013-11-21

    Theoretical calculations of the geometries, electronic structures and electronic absorption spectra of a series of covalently-linked porphyrin dimers are reported. The diporphyrins comprise 5,10,15-triphenylporphyrinatozinc(II) (ZnTriPP) units linked through the meso carbons by two-atom bridges, namely 1,2-ethanediyl (1), trans-1,2-ethenediyl (2), ethynediyl (3), 1,2-iminomethenediyl (4), and transdiazenediyl (5). The structures were optimised in toluene solvent by Density Functional Theory (DFT), using the integral equation formalism variant of the polarizable continuum model. The calculations were performed using the B3LYP functional and the 6-31G(d,p) basis set. The complete molecules were modelled, with no substitution of smaller groups on the periphery. In parallel, the compounds 2–5 were prepared by known or novel synthetic routes, to enable comparisons of experimental electronic absorption spectra with those calculated using time dependent-DFT at the same level of theory. As the ethane dimer 1 is not yet synthetically accessible, the model monomer meso-2-phenylethylZnTriPP was used for comparisons with the theoretical predictions. The results form a self-consistent set, enabling for the first time legitimate comparisons of the electronic structures of the series, especially regarding the degree to which the porphyrin p-systems interact by conjugation across the bridges. The theoretical calculations of the electronic transitions match the observed spectra in toluene to a remarkable degree, especially with respect to the peak maximum of the Q band, which represents to a large degree the energy of the HOMO–LUMO transition. The imine 4 is intrinsically polar due to the asymmetric bridge, and the HOMO is located almost exclusively on the ZnTriPP unit attached to the nitrogen of the imine, and the LUMO on the C-attached ring. Thus the Q-band transition is mapped as a comprehensive charge-transfer from the former ring to the latter. This may have consequences

  10. Synthesis, X-ray crystallography, and DFT calculations of a novel phosphoramide

    Czech Academy of Sciences Publication Activity Database

    Shariatinia, Z.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 640, č. 14 (2014), 2945-2955 ISSN 0044-2313 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : phosphoramide * x-ray structure * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.160, year: 2014

  11. DFT calculations on N2O decomposition by binuclear Fe complexes in Fe/ZSM-5

    NARCIS (Netherlands)

    Yakovlev, A.L.; Zhidomirov, G.M.; Santen, van R.A.

    2001-01-01

    N2O decomposition catalyzed by oxidized Fe clusters localized in the micropores of Fe/ZSM-5 has been studied using the DFT approach and a binuclear cluster model of the active site. Three different reaction routes were found, depending on temperature and water pressure. The results show that below

  12. Scientific periodical publications rating's calculation and analysis

    Directory of Open Access Journals (Sweden)

    B. E. Nikitin

    2017-01-01

    Full Text Available The article considers the constructing problem of the food industry journals aggregate ratings. The streamlines of the seventeen magazines on four bibliometric indexes (SCIENCE INDEX, five-year impact factor RISC given the translated version without self-citations, h-index over 10 years and Herfindahl index, which are used in the scientific electronic library elibrary.ru was used as initial data. The statement of the problem refers to multi-criteria decision-making problems. Ranking the journals in these indexes are different from each other because bibliometric indicators account different aspects of the journals. The classical approach to thisproblems solution is based on generalized criterion building in the form of an additive convolution. However, this approach requires adherence to a number of regular conditions that may not always be performed when the practical problems solution. The reductionspossibility of the considered formulation in the form of multi-criteria decision-making tasks to the problem of collective choice. The aggregated ratings of the reporting journals are calculated by using the three social choice rules – Board procedure, Copeland procedures and Kemeny median heuristic procedures. On the basis of Spearman's rank correlation determined the quantitative evaluation of the degree of intimacy built in magazines. In particular, calculated on the basis of procedure, Board and Kemeny median aggregate ratings reporting in the logs coincided. The results showed that the constructed ordering of journals on the basis of social choice rules are in good agreement with the scientific electronic library (eLIBRARY bibliometric indicators.

  13. Self-consistent DFT +U method for real-space time-dependent density functional theory calculations

    Science.gov (United States)

    Tancogne-Dejean, Nicolas; Oliveira, Micael J. T.; Rubio, Angel

    2017-12-01

    We implemented various DFT+U schemes, including the Agapito, Curtarolo, and Buongiorno Nardelli functional (ACBN0) self-consistent density-functional version of the DFT +U method [Phys. Rev. X 5, 011006 (2015), 10.1103/PhysRevX.5.011006] within the massively parallel real-space time-dependent density functional theory (TDDFT) code octopus. We further extended the method to the case of the calculation of response functions with real-time TDDFT+U and to the description of noncollinear spin systems. The implementation is tested by investigating the ground-state and optical properties of various transition-metal oxides, bulk topological insulators, and molecules. Our results are found to be in good agreement with previously published results for both the electronic band structure and structural properties. The self-consistent calculated values of U and J are also in good agreement with the values commonly used in the literature. We found that the time-dependent extension of the self-consistent DFT+U method yields improved optical properties when compared to the empirical TDDFT+U scheme. This work thus opens a different theoretical framework to address the nonequilibrium properties of correlated systems.

  14. How Many Conformations of Enzymes Should Be Sampled for DFT/MM Calculations? A Case Study of Fluoroacetate Dehalogenase

    Directory of Open Access Journals (Sweden)

    Yanwei Li

    2016-08-01

    Full Text Available The quantum mechanics/molecular mechanics (QM/MM method (e.g., density functional theory (DFT/MM is important in elucidating enzymatic mechanisms. It is indispensable to study “multiple” conformations of enzymes to get unbiased energetic and structural results. One challenging problem, however, is to determine the minimum number of conformations for DFT/MM calculations. Here, we propose two convergence criteria, namely the Boltzmann-weighted average barrier and the disproportionate effect, to tentatively address this issue. The criteria were tested by defluorination reaction catalyzed by fluoroacetate dehalogenase. The results suggest that at least 20 conformations of enzymatic residues are required for convergence using DFT/MM calculations. We also tested the correlation of energy barriers between small QM regions and big QM regions. A roughly positive correlation was found. This kind of correlation has not been reported in the literature. The correlation inspires us to propose a protocol for more efficient sampling. This saves 50% of the computational cost in our current case.

  15. Electron, hole and exciton self-trapping in germanium doped silica glass from DFT calculations with self-interaction correction

    International Nuclear Information System (INIS)

    Du Jincheng; Rene Corrales, L.; Tsemekhman, Kiril; Bylaska, Eric J.

    2007-01-01

    Density functional theory (DFT) calculations were employed to understand the refractive index change in germanium doped silica glasses for the trapped states of electronic excitations induced by UV irradiation. Local structure relaxation and excess electron density distribution were calculated upon self-trapping of an excess electron, hole, and exciton in germanium doped silica glass. The results show that both the trapped exciton and excess electron are highly localized on germanium ion and, to some extent, on its oxygen neighbors. Exciton self-trapping is found to lead to the formation of a Ge E' center and a non-bridging hole center. Electron trapping changes the GeO 4 tetrahedron structure into trigonal bi-pyramid with the majority of the excess electron density located along the equatorial line. The self-trapped hole is localized on bridging oxygen ions that are not coordinated to germanium atoms that lead to elongation of the Si-O bonds and change of the Si-O-Si bond angles. We carried out a comparative study of standard DFT versus DFT with a hybrid PBE0 exchange and correlation functional. The results show that the two methods give qualitatively similar relaxed structure and charge distribution for electron and exciton trapping in germanium doped silica glass; however, only the PBE0 functional produces the self-trapped hole

  16. Understanding the interfacial properties of graphene-based materials/BiOI heterostructures by DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Wen-Wu [Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Zhao, Zong-Yan, E-mail: zzy@kmust.edu.cn [Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Jiangsu Provincial Key Laboratory for Nanotechnology, Nanjing University, Nanjing 210093 (China)

    2017-06-01

    Highlights: • Heterostructure constructing is an effective way to enhance the photocatalytic performance. • Graphene-like materials and BiOI were in contact and formed van der Waals heterostructures. • Band edge positions of GO/g-C{sub 3}N{sub 4} and BiOI changed to form standard type-II heterojunction. • 2D materials can promote the separation of photo-generated electron-hole pairs in BiOI. - Abstract: Heterostructure constructing is a feasible and powerful strategy to enhance the performance of photocatalysts, because they can be tailored to have desirable photo-electronics properties and couple distinct advantageous of components. As a novel layered photocatalyst, the main drawback of BiOI is the low edge position of the conduction band. To address this problem, it is meaningful to find materials that possess suitable band gap, proper band edge position, and high mobility of carrier to combine with BiOI to form hetertrostructure. In this study, graphene-based materials (including: graphene, graphene oxide, and g-C{sub 3}N{sub 4}) were chosen as candidates to achieve this purpose. The charge transfer, interface interaction, and band offsets are focused on and analyzed in detail by DFT calculations. Results indicated that graphene-based materials and BiOI were in contact and formed van der Waals heterostructures. The valence and conduction band edge positions of graphene oxide, g-C{sub 3}N{sub 4} and BiOI changed with the Fermi level and formed the standard type-II heterojunction. In addition, the overall analysis of charge density difference, Mulliken population, and band offsets indicated that the internal electric field is facilitate for the separation of photo-generated electron-hole pairs, which means these heterostructures can enhance the photocatalytic efficiency of BiOI. Thus, BiOI combines with 2D materials to construct heterostructure not only make use of the unique high electron mobility, but also can adjust the position of energy bands and

  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. DFT-GIAO calculation of properties of {sup 19}F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)

    Energy Technology Data Exchange (ETDEWEB)

    Mejia-Urueta, Rafael; Mestre-Quintero, Kleyber; Vivas-Reyes, Ricardo, E-mail: rvivasr@unicartagena.edu.co [Grupo de Quimica Cuantica y Teorica, Facultad de Ciencias Exactas y Naturales, Universidad de Cartagena, Cartagena (Colombia)

    2011-09-15

    Perfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, {sup 19}F nuclear magnetic resonance (NMR {sup 19}F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of {sup 19}F NMR was performed. In this study we have determined the shielding constant ({sigma}) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The {sigma} calculations were made at vacuum and in presence of a solvent. The values of chemical shifts ({delta}), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl{sub 3}), acetone (CH{sub 3}COCH{sub 3}) and methanol (CH{sup 3}OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS). (author)

  19. DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)

    International Nuclear Information System (INIS)

    Mejia-Urueta, Rafael; Mestre-Quintero, Kleyber; Vivas-Reyes, Ricardo

    2011-01-01

    Perfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, 19 F nuclear magnetic resonance (NMR 19 F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of 19 F NMR was performed. In this study we have determined the shielding constant (σ) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The σ calculations were made at vacuum and in presence of a solvent. The values of chemical shifts (δ), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl 3 ), acetone (CH 3 COCH 3 ) and methanol (CH 3 OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS). (author)

  20. DFT calculations of electronic and optical properties of SrS with LDA, GGA and mGGA functionals

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Shatendra, E-mail: shatendra@gmai.com [University Science Instrumentation Centre, Jawaharlal Nehru University, New Delhi-110067 (India); Sharma, Jyotsna [School of Basic & Applied Sciences, K. R. Mangalam University, Sohna Road, Gurgaon-122103 (India); Sharma, Yogita [Department of Applied Sciences, KIIT, Sohna Road, Gurgaon-122103 (India)

    2016-05-06

    The theoretical investigations of electronic and optical properties of SrS are made using the first principle DFT calculations. The calculations are performed for the local-density approximation (LDA), generalized gradient approximation (GGA) and for an alternative form of GGA i.e. metaGGA for both rock salt type (B1, Fm3m) and cesium chloride (B2, Pm3m) structures. The band structure, density of states and optical spectra are calculated under various available functional. The calculations with LDA and GGA functional underestimate the values of band gaps with all functional, however the values with mGGA show reasonably good agreement with experimental and those calculated by using other methods.

  1. Experimental and semi-empirical and DFT calculational studies on (E)-2-((2-morpholinoethyliminio)methyl)-4-nitrophenolate

    International Nuclear Information System (INIS)

    Alpaslan, Y. B.; Agar, E.; Ersahin, F.; Iskeleli, N. O.; Oeztekin, E.

    2010-01-01

    The molecular and crystal structure of the title compound, C 1 3H 1 7N 3 O 4 , has been determined by X-ray single crystal diffraction technique. The compound crystallizes in the triclinic, space group P-1 with unit cell dimensions a=5.3520(4), b=10.9011(8), c=12.4537(9)A 0 , Mr=279.30, V=675.91(9)A 03 , Z=2, R1=0.037 and wR 2 =0.097. The molecule adopts a zwitterionic form, stabilized by an intramolecular N + -H 2 O- type ionic weak hydrogen bond. The molecule pack via intermolecular N-H 2 O hydrogen bonds which, together with an intramolecular N + -H 2 O- bond. Calculational studies were performed by using AM1, PM3, semi-empirical and DFT methods. Geometry optimizations of compound have been carried out by using three semi-empirical methods and DFT method and bond lengths, bond and torsion angles of title compound have been determined. Atomic charge distribution have been obtained from DFT. In order to determine conformational flexibility on the molecule, molecular energy profile of the title compound was obtained with respect to the selected torsion angle T(C2-C1-C7-N1), which is varied from -180 0 degree to +180 0 degree in every 10 via PM3 semi-empirical method.

  2. Proton affinities of maingroup-element hydrides and noble gases: trends across the periodic table, structural effects, and DFT validation.

    Science.gov (United States)

    Swart, Marcel; Rösler, Ernst; Bickelhaupt, F Matthias

    2006-10-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal neutral bases across the periodic system using the generalized gradient approximation (GGA) of the density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities: BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 2.0 kcal/mol for the proton affinity at 298 K with respect to experiment, and 1.2 kcal/mol with high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the neutral bases constituted by all maingroup-element hydrides of groups 15-17 and the noble gases, that is, group 18, and periods 1-6. We have also studied the effect of step-wise methylation of the protophilic center of the second- and third-period bases. Copyright 2006 Wiley Periodicals, Inc.

  3. Proton Affinities of Anionic Bases:  Trends Across the Periodic Table, Structural Effects, and DFT Validation.

    Science.gov (United States)

    Swart, Marcel; Bickelhaupt, F Matthias

    2006-03-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities:  BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 1.6 kcal/mol for the proton affinity at 0 K with respect to high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the anionic conjugate bases of all main-group-element hydrides of groups 14-17 and periods 2-6. We have also studied the effect of stepwise methylation of the protophilic center of the second- and third-period bases.

  4. PBE-DFT theoretical study of organic photovoltaic materials based on thiophene with 1D and 2D periodic boundary conditions

    Science.gov (United States)

    Saïl, K.; Bassou, G.; Gafour, M. H.; Miloua, F.

    2015-12-01

    Conjugated organic systems such as thiophene are interesting topics in the field of organic solar cells. We theoretically investigate π-conjugated polymers constituted by n units ( n = 1-11) based on the thiophene (Tn) molecule. The computations of the geometries and electronic structures of these compounds are performed using the density functional theory (DFT) at the 6-31 G( d, p) level of theory and the Perdew-Burke-Eenzerhof (PBE) formulation of the generalized gradient approximation with periodic boundary conditions (PBCs) in one (1D) and two (2D) dimensions. Moreover, the electronic properties (HOCO, LUCO, E gap, V oc, and V bi) are determined from 1D and 2D PBC to understand the effect of the number of rings in polythiophene. The absorption properties—excitation energies ( E ex), the maximal absorption wavelength (λmax), oscillator strengths, and light harvesting—efficiency are studied using the time-dependent DFT method. Our studies show that changing the number of thiophene units can effectively modulate the electronic and optical properties. On the other hand, our work demonstrates the efficiency of theoretical calculation in the PBCs.

  5. PBE–DFT theoretical study of organic photovoltaic materials based on thiophene with 1D and 2D periodic boundary conditions

    International Nuclear Information System (INIS)

    Saïl, K.; Bassou, G.; Gafour, M. H.; Miloua, F.

    2015-01-01

    Conjugated organic systems such as thiophene are interesting topics in the field of organic solar cells. We theoretically investigate π-conjugated polymers constituted by n units (n = 1–11) based on the thiophene (Tn) molecule. The computations of the geometries and electronic structures of these compounds are performed using the density functional theory (DFT) at the 6–31 G(d, p) level of theory and the Perdew–Burke–Eenzerhof (PBE) formulation of the generalized gradient approximation with periodic boundary conditions (PBCs) in one (1D) and two (2D) dimensions. Moreover, the electronic properties (HOCO, LUCO, E gap , V oc , and V bi ) are determined from 1D and 2D PBC to understand the effect of the number of rings in polythiophene. The absorption properties—excitation energies (E ex ), the maximal absorption wavelength (λ max ), oscillator strengths, and light harvesting—efficiency are studied using the time-dependent DFT method. Our studies show that changing the number of thiophene units can effectively modulate the electronic and optical properties. On the other hand, our work demonstrates the efficiency of theoretical calculation in the PBCs

  6. PBE–DFT theoretical study of organic photovoltaic materials based on thiophene with 1D and 2D periodic boundary conditions

    Energy Technology Data Exchange (ETDEWEB)

    Saïl, K., E-mail: sailkari7@yahoo.com; Bassou, G. [Université Djillali Liabès, Laboratoire de Microscopie, Microanalyse de la Matière et Spectroscopie Moléculaire (L2MSM), Faculté des Sciences Exactes (Algeria); Gafour, M. H. [Centre Universitaire Ahmed Zabana de Rélizane, Institut des Sciences Exactes et Sciences de la Nature et de la Vie, Département de Chimie (Algeria); Miloua, F. [Université Djillali Liabès, Laboratoire de Microscopie, Microanalyse de la Matière et Spectroscopie Moléculaire (L2MSM), Faculté des Sciences Exactes (Algeria)

    2015-12-15

    Conjugated organic systems such as thiophene are interesting topics in the field of organic solar cells. We theoretically investigate π-conjugated polymers constituted by n units (n = 1–11) based on the thiophene (Tn) molecule. The computations of the geometries and electronic structures of these compounds are performed using the density functional theory (DFT) at the 6–31 G(d, p) level of theory and the Perdew–Burke–Eenzerhof (PBE) formulation of the generalized gradient approximation with periodic boundary conditions (PBCs) in one (1D) and two (2D) dimensions. Moreover, the electronic properties (HOCO, LUCO, E{sub gap}, V{sub oc}, and V{sub bi}) are determined from 1D and 2D PBC to understand the effect of the number of rings in polythiophene. The absorption properties—excitation energies (E{sub ex}), the maximal absorption wavelength (λ{sub max}), oscillator strengths, and light harvesting—efficiency are studied using the time-dependent DFT method. Our studies show that changing the number of thiophene units can effectively modulate the electronic and optical properties. On the other hand, our work demonstrates the efficiency of theoretical calculation in the PBCs.

  7. DFT calculation and experimental validation on the interactions of bis(trifluoromethylsulfonyl)imide and hexafluorophosphate with cesium

    Science.gov (United States)

    Sun, Taoxiang; Duan, Wuhua; Wang, Yaxing; Hu, Shaowen; Wang, Shuao; Chen, Jing; Shen, Xinghai

    2017-11-01

    Bis(trifluoromethylsulfonyl)imide (NTf2-) and hexafluorophosphate (PF6-) are the most frequently used anions for hydrophobic ionic liquids (ILs) which have been considered as promising solvents in the extraction of cesium ions. The interactions of NTf2- and PF6- with Cs+ were explored in this work. The results of DFT calculation indicated that both Cs+ and Cs(18C6)+ prefer to interact with two NTf2- or PF6- anions in gas phase, where 18C6 is 18-crown-6. The complex of Cs(NTf2)2- was observed in electrospray ionization mass spectrometry (ESI-MS), and the complexes of [Cs(18C6)NTf2]2 and [Cs(18C6)PF6]2 were crystallized in which Cs(18C6)+ interacted with two anions. The interactions of NTf2- with cesium resulted in a synergistic effect between dicyclohexano-18-crown-6 (DCH18C6) and NTf2- in the extraction of Cs+ using n-octanol as diluent. However, DFT calculation revealed that the complex Cs(DCH18C6)+ interacted with one NTf2- anion was more thermodynamically stable than that with two anions in organic phase, different from that in gas phase.

  8. Structure evolution of mononuclear tungsten and molybdenum species in the protonation process: Insight from FPMD and DFT calculations

    Science.gov (United States)

    Zhang, Ning; Yi, Haibo; Zeng, Dewen; Zhao, Zhongwei; Wang, Wenlei; Costanzo, Francesca

    2018-03-01

    In this work, we apply static density functional theory (DFT) calculations, as well as classical and first-principles molecular dynamics (FPMD) simulations, using the free-energy perturbation method to study the protonation ability, active site and structures of W(VI) and Mo(VI) in acidic aqueous solution. Using FPMD simulations, utilizing the pKa's calculation technique, we concluded that the octahedral WO2(OH)2(H2O)2 is the true formula for tungstic acid (H2WO4), and the hydroxyl ligands are the acidic site. This aqueous structure of H2WO4 is analogous to the previously reported structure of molybdic acid (H2MoO4). The FPMD trajectories of the tungstic acid deprotonation show that the mono-protonated monotungstate ion (HWO4-) may partially exist as a five-coordinated WO3(OH)(H2O)- species except for the four-coordinated WO3(OH)- species. This result is supported by DFT calculations, with an isoenergetic point (ΔE = 1.9 kcal·mol-1) for the WO3(OH)(H2O)- and WO3(OH)- species, when explicit solvent molecules are taken into account. In contrast, for the H2MoO4 acid, FPMD trajectories during the deprotonation process show that two H2O ligands immediately escape from the first coordinated sphere of Mo(VI) to form the four-coordinated MoO3(OH)- species. This difference indicates that structural expansion of W(VI) began in the first protonated step, while that of Mo(VI) only occurs in the second step. In addition, our calculated first and second acid constants for tungstic acid are higher than previously reported values for molybdic acid. This result suggests that WO42- is more easily protonated than the MoO42- anion in the same acidic solution, which is further confirmed by DFT calculations of hydrated oxoanions and its protonated species, based upon the hydration energy.

  9. Electronic structure calculation of Sr2CoWO6 double perovskite using DFT+U

    Science.gov (United States)

    Mandal, Golak; Jha, Dhiraj; Himanshu, A. K.; Ray, Rajyavardhan; Mukherjee, P.; Das, Nisith; Singh, B. K.; Sreenivas, K.; Singh, M. N.; Sinha, A. K.

    2018-04-01

    Using the synchrotron and Raman spectroscopy we measured the lattice parameter and Raman modes of the half-metallic (HM) Sr2CoWO6 (SCoW) synthesied by the solid state reaction technique.. The physical properties of SCoW are studies within the framework of density function theory (DFT) under the generalised gradient approximation (GGA) of Perdew, Bruke, and Ernzerhof both by itself and including a coulomb repulsion via the Hubbard approach or GGA+U. Our results states that Sr2CoWO6 material behaves as insulators for the spin-up orientation and spindown orientation as found for the half metallic systems and at U = 0.06eV the ground state of spin up channel being insulating with spin gap of 2.27eV comparable to the experimental Band gap (BG).

  10. Understanding the difference in cohesive energies between alpha and beta tin in DFT calculations

    International Nuclear Information System (INIS)

    Legrain, Fleur; Manzhos, Sergei

    2016-01-01

    The transition temperature between the low-temperature alpha phase of tin to beta tin is close to the room temperature (T_α_β = 13"0C), and the difference in cohesive energy of the two phases at 0 K of about ΔE_c_o_h =0.02 eV/atom is at the limit of the accuracy of DFT (density functional theory) with available exchange-correlation functionals. It is however critically important to model the relative phase energies correctly for any reasonable description of phenomena and technologies involving these phases, for example, the performance of tin electrodes in electrochemical batteries. Here, we show that several commonly used and converged DFT setups using the most practical and widely used PBE functional result in ΔE_c_o_h ≈0.04 eV/atom, with different types of basis sets and with different models of core electrons (all-electron or pseudopotentials of different types), which leads to a significant overestimation of T_α_β. We show that this is due to the errors in relative positions of s and p –like bands, which, combined with different populations of these bands in α and β Sn, leads to overstabilization of alpha tin. We show that this error can be effectively corrected by applying a Hubbard +U correction to s –like states, whereby correct cohesive energies of both α and β Sn can be obtained with the same computational scheme. We quantify for the first time the effects of anharmonicity on ΔE_c_o_h and find that it is negligible.

  11. 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.

  12. Understanding the difference in cohesive energies between alpha and beta tin in DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Legrain, Fleur; Manzhos, Sergei, E-mail: mpemanzh@nus.edu.sg [Department of Mechanical Engineering, National University of Singapore, 117576 (Singapore)

    2016-04-15

    The transition temperature between the low-temperature alpha phase of tin to beta tin is close to the room temperature (T{sub αβ} = 13{sup 0}C), and the difference in cohesive energy of the two phases at 0 K of about ΔE{sub coh} =0.02 eV/atom is at the limit of the accuracy of DFT (density functional theory) with available exchange-correlation functionals. It is however critically important to model the relative phase energies correctly for any reasonable description of phenomena and technologies involving these phases, for example, the performance of tin electrodes in electrochemical batteries. Here, we show that several commonly used and converged DFT setups using the most practical and widely used PBE functional result in ΔE{sub coh} ≈0.04 eV/atom, with different types of basis sets and with different models of core electrons (all-electron or pseudopotentials of different types), which leads to a significant overestimation of T{sub αβ}. We show that this is due to the errors in relative positions of s and p –like bands, which, combined with different populations of these bands in α and β Sn, leads to overstabilization of alpha tin. We show that this error can be effectively corrected by applying a Hubbard +U correction to s –like states, whereby correct cohesive energies of both α and β Sn can be obtained with the same computational scheme. We quantify for the first time the effects of anharmonicity on ΔE{sub coh} and find that it is negligible.

  13. Experimental and semi-empirical and DFT calculational studies on (e)-2-(1-(2-(4-methylphenylsulfonamido) ethyliminio) ethyl) phenolate

    International Nuclear Information System (INIS)

    Alpaslan, G.; Agar, E.; Ersahin, F.; Isik, S.; Erdoenmez, A.

    2010-01-01

    The molecular and crystal structure of the title compound, C 1 7H 2 0N 2 O 3 S, has been determined by X-ray single crystal diffraction technique. The compound crystallizes in the monoclinic, space group P2 1 /n with unit cell dimensions a=11.4472(6), b=11.1176(4), c=13.4873(7)A 0 , M r =332.41, V=1639.36(13)A 03 , Z=4, R 1 =0.034 and wR 2 =0.097. The molecule adopts a zwitterionic form, stabilized by an intramolecular N + -H 2 O - type ionic weak hydrogen bond. The molecule pack via intermolecular N-H 2 O hydrogen bonds which, together with an intramolecular N + -H 2 O - bond, form an S(6)R 2 4 (4)S(6) motif. Calculational studies were performed by using AM1, PM3 semi-empirical and DFT methods. Geometry optimizations of compound have been carried out by using three semi-empirical methods and DFT method and bond lengths, bond and torsion angles of title compound have been determined. Atomic charge distribution have been obtained from AM1, PM3 and DFT. In order to determine conformational flexibility on the molecule, molecular energy profile of the title compound was obtained with respect to the selected torsion angle T(N1-C9-C10-N2), which is varied from -180 degrees to +180 degrees in every 10 via PM3 semi-empirical method.

  14. Studies of the electronic structure and biological activity of chosen 1,4-benzodiazepines by {sup 35}Cl NQR spectroscopy and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Bronisz, K. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland); Ostafin, M. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland)], E-mail: ostifnqr@amu.edu.pl; Poleshchuk, O. Kh. [Department of Chemistry, Tomsk Pedagogical University, Komsomolskii 75, 634041 Tomsk (Russian Federation); Mielcarek, J. [Faculty of Pharmacy, University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan (Poland); Nogaj, B. [Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan (Poland)

    2006-11-08

    Selected derivatives of 1,4-benzodiazepine: lorazepam, lormetazepam, oxazepam and temazepam, used as active substances in anxiolytic drugs, have been studied by {sup 35}Cl NQR method in order to find the correlation between electronic structure and biological activity. The {sup 35}Cl NQR resonance frequencies ({nu} {sub Q}) measured at 77 K have been correlated with the following parameters characterising their biological activity: biological half-life period (t {sub 0.5}), affinity to benzodiazepine receptor (IC{sub 50}) and mean dose equivalent. The results of experimental study of some benzodiazepine derivatives by nuclear quadrupole resonance of {sup 35}Cl nuclei are compared with theoretical results based on DFT calculations which were carried out by means of Gaussian'98 W software.

  15. Calculation of positron characteristics for elements of the periodic table

    International Nuclear Information System (INIS)

    Campillo Robles, J M; Ogando, E; Plazaola, F

    2011-01-01

    Positron characteristics have been calculated in bulk and monovacancies for most of the elements of the periodic table. Self-consistent and non-self-consistent schemes have been used for the calculation of the electronic structure in the solid, and different parametrizations for the positron enhancement factor and correlation energy. As it is known, positron lifetimes in bulk show a periodic behaviour with atomic number. These calculations also confirm that monovacancy lifetimes follow the same behaviour. The results obtained have been compared with selected experimental lifetime data, which confirms the calculated theoretical trends. Positron binding energies to a monovacancy have been calculated also for most of the elements of the periodic table. The binding energy shows a periodic behaviour with atomic number too.

  16. Electronic structure and optical properties of Cs2HgI4: Experimental study and band-structure DFT calculations

    Science.gov (United States)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Shkumat, P. N.; Myronchuk, G. L.; Khvyshchun, M.; Fedorchuk, A. O.; Parasyuk, O. V.; Khyzhun, O. Y.

    2015-04-01

    High-quality single crystal of cesium mercury tetraiodide, Cs2HgI4, has been synthesized by the vertical Bridgman-Stockbarger method and its crystal structure has been refined. In addition, electronic structure and optical properties of Cs2HgI4 have been studied. For the crystal under study, X-ray photoelectron core-level and valence-band spectra for pristine and Ar+-ion irradiated surfaces have been measured. The present X-ray photoelectron spectroscopy (XPS) results indicate that the Cs2HgI4 single crystal surface is very sensitive with respect to Ar+ ion-irradiation. In particular, Ar+ bombardment of the single crystal surface alters the elemental stoichiometry of the Cs2HgI4 surface. To elucidate peculiarities of the energy distribution of the electronic states within the valence-band and conduction-band regions of the Cs2HgI4 compound, we have performed first-principles band-structure calculations based on density functional theory (DFT) as incorporated in the WIEN2k package. Total and partial densities of states for Cs2HgI4 have been calculated. The DFT calculations reveal that the I p states make the major contributions in the upper portion of the valence band, while the Hg d, Cs p and I s states are the dominant contributors in its lower portion. Temperature dependence of the light absorption coefficient and specific electrical conductivity has been explored for Cs2HgI4 in the temperature range of 77-300 K. Main optical characteristics of the Cs2HgI4 compound have been elucidated by the first-principles calculations.

  17. 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.

  18. Exploration of sensing of nitrogen dioxide and ozone molecules using novel TiO2/Stanene heterostructures employing DFT calculations

    Science.gov (United States)

    Abbasi, Amirali; Sardroodi, Jaber Jahanbin

    2018-06-01

    Based on the density functional theory (DFT) calculations, we explored the sensing capabilities and electronic structures of TiO2/Stanene heterostructures as novel and highly efficient materials for detection of toxic NO2 and O3 molecules in the environment. Studied gas molecules were positioned at different sites and orientations towards the nanocomposite, and the adsorption process was examined based on the most stable structures. We found that both of these molecules are chemically adsorbed on the TiO2/Stanene heterostructures. The calculations of the adsorption energy indicate that the fivefold coordinated titanium sites of the TiO2/Stanene are the most stable sites for the adsorption of NO2 and O3 molecules. The side oxygen atoms of the gas molecules were found to be chemically bonded to these titanium atoms. The adsorption of gas molecules is an exothermic process, and the adsorption on the pristine nanocomposite is more favorable in energy than that on the nitrogen-doped nanocomposite. The effects of van der Waals interactions were taken into account, which indicate the adsorption energies were increased for the most sable configurations. The gas sensing response and charge transfers were analyzed in detail. The pristine nanocomposites have better sensing response than the doped ones. The spin density distribution plots indicate that the magnetization was mainly located over the adsorbed gas molecules. Mulliken charge analysis reveals that both NO2 and O3 molecules behave as charge acceptors, as evidenced by the accumulation of electronic charges on the adsorbed molecules predicted by charge density difference calculations. Our DFT results provide a theoretical basis for an innovative gas sensor system designed from a sensitive TiO2/Stanene heterostructures for efficient detection of harmful air pollutants such as NO2 and O3.

  19. Electronic and optical properties of 2D graphene-like ZnS: DFT calculations

    International Nuclear Information System (INIS)

    Lashgari, Hamed; Boochani, Arash; Shekaari, Ashkan; Solaymani, Shahram; Sartipi, Elmira; Mendi, Rohollah Taghavi

    2016-01-01

    Graphical abstract: - Highlights: • DFT has been applied to investigate the optical properties of 2D-ZnS and 3D-ZnS. • The electronic and the optical properties of 3D-ZnS and 2D-ZnS are compared. • At visible range of energies the transparency of 2D-ZnS is more than the 3D. - Abstract: Density-functional theory has been applied to investigate the electronic and optical properties of graphene-like two-dimensional ZnS in the (0001) direction of its Wurtzite phase. A comparison with 3D-ZnS has been carried out within the PBE- and EV-GGA. The electronic properties of 2D- and 3D-ZnS have been derived by the examination of the electronic band structures and density of states. The optical properties have been determined through the study of the dielectric function, reflectivity, electron loss function, refractive and extinction indices, the absorption index and optical conductivity. It is found that the transparency of 2D-ZnS is greater than the 3D over the visible range. A thorough study of the dielectric function has been performed so that the peaks and the transition bands have been specified. The electron loss function demonstrates that the plasmonic frequency for 2D- and 3D-ZnS is accrued at 11.22 and 19.93 eV within the PBE-GGA, respectively.

  20. 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.

  1. Calculation of coupling factor for double-period accelerating structure

    International Nuclear Information System (INIS)

    Bian Xiaohao; Chen Huaibi; Zheng Shuxin

    2005-01-01

    In the design of the linear accelerating structure, the coupling factor between cavities is a crucial parameter. The error of coupling factor accounts for the electric or magnetic field error mainly. To accurately design the coupling iris, the accurate calculation of coupling factor is essential. The numerical simulation is widely used to calculate the coupling factor now. By using MAFIA code, two methods have been applied to calculate the dispersion characteristics of the single-period structure, one method is to simulate the traveling wave mode by the period boundary condition; another method is to simulate the standing wave mode by the electrical boundary condition. In this work, the authors develop the two methods to calculate the coupling factor of double-period accelerating structure. Compared to experiment, the results for both methods are very similar, and in agreement with measurement within 15% deviation. (authors)

  2. DFT Calculations using WIEN2K to determine oxygen defect structure of rare earth doped ceria

    CERN Document Server

    Khalife, Ali Rida

    2014-01-01

    We perform density functional calculations using the program WIEN2K in order to study oxygen vacancies in rare earth doped ceria. The calculation for all rare earth elements were prepared, however only those foe Cadmium and Europium were performed due to lack of time. Also a short description of my stay at CERN was presented

  3. Infrared and Raman spectra, DFT-calculations and spectral assignments of germacyclohexane

    Energy Technology Data Exchange (ETDEWEB)

    Aleksa, V., E-mail: valdemaras.aleksa@ff.vu.lt; Ozerenskis, D.; Pucetaite, M.; Sablinskas, V. [Faculty of Physics, Vilnius University, Sauletekio av. 9, block 3, Vilnius, LT-10222 (Lithuania); Cotter, C.; Guirgis, G. A. [Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424 (United States)

    2015-03-30

    Raman spectra of germacyclohexane in liquid and solid states were recorded and depolarization data obtained. Infrared absorption spectra of the vapor and liquid have been studied. The wavenumbers of the vibrational modes were derived in the harmonic and anharmonic approximation in B3LYP/ccpVTZ calculations. According to the calculations, germacyclohexane exists in the stable chair conformation, whereas a possible twist form should have more than 15 kJ·mol{sup -1} higher enthalpy of formation what makes this conformer experimentally not observable. The 27 A' and 21 A'' fundamentals were assigned on the basis of the calculations and infrared and Raman band intensities, contours of gas phase infrared spectral bands and Raman depolarization measurements. An average discrepancy of ca. 0.77 % was found between the observed and the calculated anharmonic wavenumbers for the 48 modes. Substitution of carbon atom with Ge atom in the cyclohexane ring is reasoning flattening of the ring.

  4. Electronically excited states of chloroethylenes: Experiment and DFT calculations in comparison

    International Nuclear Information System (INIS)

    Khvostenko, O.G.

    2014-01-01

    Highlights: • B3LYP/6-311 + G(d,p) calculations of chloroethylenes molecules were performed. • Calculations were correlated with experiment on the molecules ground and excited states. • The general pattern of electron structure of chloroethylenes was obtained. • Necessity of this data for chloroethylenes negative ions study was noted. - Abstract: B3LYP/6-311 + G(d,p) calculations of ground and electronically excited states of ethylene, chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene-cis, 1,2-dichloroethylene-trans trichloroethylene and tetrachloroethylene molecules have been performed. Molecular orbitals images and orbital correlation diagram are given. The calculation results for chloroethylenes electronically excited states were compared with experimental data from the energy-loss spectra obtained and generally considered previously by C.F. Koerting, K.N. Walzl and A. Kupperman. Several new additional triplet and singlet transitions were pointed out in these spectra considering the calculation results. The finding of the additional transitions was supported by the UV absorption spectrum of trichloroethylene recorded in big cuvette (10 cm), where the first three triplet and two low-intensive forbidden singlet transitions were registered. The first triplet of this compound was recorded to be at the same energy as was found with the energy-loss spectroscopy

  5. Electronically excited states of chloroethylenes: Experiment and DFT calculations in comparison

    Energy Technology Data Exchange (ETDEWEB)

    Khvostenko, O.G., E-mail: khv@mail.ru

    2014-08-15

    Highlights: • B3LYP/6-311 + G(d,p) calculations of chloroethylenes molecules were performed. • Calculations were correlated with experiment on the molecules ground and excited states. • The general pattern of electron structure of chloroethylenes was obtained. • Necessity of this data for chloroethylenes negative ions study was noted. - Abstract: B3LYP/6-311 + G(d,p) calculations of ground and electronically excited states of ethylene, chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene-cis, 1,2-dichloroethylene-trans trichloroethylene and tetrachloroethylene molecules have been performed. Molecular orbitals images and orbital correlation diagram are given. The calculation results for chloroethylenes electronically excited states were compared with experimental data from the energy-loss spectra obtained and generally considered previously by C.F. Koerting, K.N. Walzl and A. Kupperman. Several new additional triplet and singlet transitions were pointed out in these spectra considering the calculation results. The finding of the additional transitions was supported by the UV absorption spectrum of trichloroethylene recorded in big cuvette (10 cm), where the first three triplet and two low-intensive forbidden singlet transitions were registered. The first triplet of this compound was recorded to be at the same energy as was found with the energy-loss spectroscopy.

  6. Positron lifetime calculation for the elements of the periodic table.

    Science.gov (United States)

    Campillo Robles, J M; Ogando, E; Plazaola, F

    2007-04-30

    Theoretical positron lifetime values have been calculated systematically for most of the elements of the periodic table. Self-consistent and non-self-consistent schemes have been used for the calculation of the electronic structure in the solid, as well as different parametrizations for the positron enhancement factor and correlation energy. The results obtained have been studied and compared with experimental data, confirming the theoretical trends. As is known, positron lifetimes in bulk show a periodic behaviour with atomic number. These calculations also confirm that monovacancy lifetimes follow the same behaviour. The effects of enhancement factors used in calculations have been commented upon. Finally, we have analysed the effects that f and d electrons have on positron lifetimes.

  7. Positron lifetime calculation for the elements of the periodic table

    International Nuclear Information System (INIS)

    Robles, J M Campillo; Ogando, E; Plazaola, F

    2007-01-01

    Theoretical positron lifetime values have been calculated systematically for most of the elements of the periodic table. Self-consistent and non-self-consistent schemes have been used for the calculation of the electronic structure in the solid, as well as different parametrizations for the positron enhancement factor and correlation energy. The results obtained have been studied and compared with experimental data, confirming the theoretical trends. As is known, positron lifetimes in bulk show a periodic behaviour with atomic number. These calculations also confirm that monovacancy lifetimes follow the same behaviour. The effects of enhancement factors used in calculations have been commented upon. Finally, we have analysed the effects that f and d electrons have on positron lifetimes

  8. Dielectric response of periodic systems from quantum Monte Carlo calculations.

    Science.gov (United States)

    Umari, P; Willamson, A J; Galli, Giulia; Marzari, Nicola

    2005-11-11

    We present a novel approach that allows us to calculate the dielectric response of periodic systems in the quantum Monte Carlo formalism. We employ a many-body generalization for the electric-enthalpy functional, where the coupling with the field is expressed via the Berry-phase formulation for the macroscopic polarization. A self-consistent local Hamiltonian then determines the ground-state wave function, allowing for accurate diffusion quantum Monte Carlo calculations where the polarization's fixed point is estimated from the average on an iterative sequence, sampled via forward walking. This approach has been validated for the case of an isolated hydrogen atom and then applied to a periodic system, to calculate the dielectric susceptibility of molecular-hydrogen chains. The results found are in excellent agreement with the best estimates obtained from the extrapolation of quantum-chemistry calculations.

  9. PEEM microscopy and DFT calculations of catalytically active platinum surfaces and interfaces

    International Nuclear Information System (INIS)

    Spiel, C.

    2012-01-01

    CO, pO2, T) in one of both steady states depending on the system's prehistory. The bistable reaction kinetics can be studied globally with QMS, and the positions of the global transition points τ A and τ B in parameter space can be obtained this way. Based on a series of experiments, a global kinetic phase diagram can be established that is a useful tool to characterize the average behavior of a heterogeneous sample. In turn, using PEEM the kinetic phase transition points can also be obtained in a laterally-resolved way for each individual surface domain by analyzing local PEEM intensity variations. In the present work, QMS and PEEM experiments were performed, from which both global and laterally-resolved kinetic phase diagrams of polycrystalline platinum foil and, correspondingly, its [100]-, [110]- and [111]-oriented domains were obtained. The kinetic phase diagrams were measured both for constant oxygen partial pressure and varying temperatures as well as for constant temperature and varying oxygen partial pressure. Besides that, kinetic transitions that trigger catalytic ignition and extinction of the CO oxidation reaction were also studied in situ on the same sample and compared to results from experiments using field ion microscopy (FIM). The second part of this thesis consisted of a theoretical study of CeO 2 monolayers adsorbed on the Pt(111) surface. For this purpose, density functional theory (DFT) was applied in the implementation of the WIEN2k software package. (author) [de

  10. A novel alkaloid isolated from Crotalaria paulina and identified by NMR and DFT calculations

    Science.gov (United States)

    Oliveira, Ramon Prata; Demuner, Antonio Jacinto; Alvarenga, Elson Santiago; Barbosa, Luiz Claudio Almeida; de Melo Silva, Thiago

    2018-01-01

    Pyrrolizidine alkaloids (PAs) are secondary metabolites found in Crotalaria genus and are known to have several biological activities. A novel macrocycle bislactone alkaloid, coined ethylcrotaline, was isolated and purified from the aerial parts of Crotalaria paulina. The novel macrocycle was identified with the aid of high resolution mass spectrometry and advanced nuclear magnetic resonance techniques. The relative stereochemistry of the alkaloid was defined by comparing the calculated quantum mechanical hydrogen and carbon chemical shifts of eight candidate structures with the experimental NMR data. The best fit between the eight candidate structures and the experimental NMR chemical shifts was defined by the DP4 statistical analyses and the Mean Absolute Error (MAE) calculations.

  11. DFT calculations on 1-hetero-2,5-cyclohexadiene-1-oxide ...

    African Journals Online (AJOL)

    Isodesmic reactions to determine the stabilities of XOand X are considered. Nuclear independent chemical shifts, NICS, are calculated for the investigation of the homo-aromatic character of XOand X. The optimised geometries show the bonding in the molecules is explicable in terms of basic chemical concepts. The atomic ...

  12. The determination of sulfoxide configuration in six-membered rings using NMR specroscopy and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Pohl, Radek; Slavětínská, Lenka; Janků, J.; Buděšínský, Miloš

    2011-01-01

    Roč. 22, č. 3 (2011), s. 356-366 ISSN 0957-4166 R&D Projects: GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * calculation of NMR parameters * sulfoxides * configuration Subject RIV: CC - Organic Chemistry Impact factor: 2.652, year: 2011

  13. Scaling tests of a new algorithm for DFT hybrid-functional calculations on Trinity Haswell

    Energy Technology Data Exchange (ETDEWEB)

    Wright, Alan F. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Modine, Normand A. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-09-01

    We show scaling results for materials of interest in Sandia Radiation-Effects and High-Energy-Density-Physics Mission Areas. Each timing is from a self-consistent calculation for bulk material. Two timings are given: (1) walltime for the construction of the CR exchange operator (Exchange-Operator) and (2) walltime for everything else (non-Exchange-Operator).

  14. Synthesis, crystal structure and DFT calculations of a new Hg (II) metal-organic polymer

    Czech Academy of Sciences Publication Activity Database

    Mirtamizdoust, B.; Roodsari, M.S.; Shaabani, B.; Dušek, Michal; Fejfarová, Karla

    2016-01-01

    Roč. 15, č. 3 (2016), s. 257-266 ISSN 1024-1221 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : mercury (II) iodide * coordination polymer * square planar * tetrahedral geometry * density functional calculation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.565, year: 2016

  15. Relativistic DFT calculations of hyperfine coupling constants in the 5d hexafluorido complexes

    DEFF Research Database (Denmark)

    Haase, Pi Ariane Bresling; Repisky, Michal; Komorovsky, Stanislav

    2018-01-01

    We have investigated the performance of the most popular relativistic density functional theory methods, zeroth order regular approximation (ZORA) and 4-component Dirac-Kohn-Sham (DKS), in the calculation of the recently measured hyperfine coupling constants of ReIV and IrIV in their hexafluorido...

  16. Positron lifetime calculation of the elements of the periodic table

    International Nuclear Information System (INIS)

    Campillo, J.M.; Plazaola, F.

    2001-01-01

    The classification of the elements has been one of the major achievements of Science. Since then the resulting periodic order has been most strikingly reflected in a quantitative manner by most of the physical properties of the elements. The aim of this paper is to show the strong relation between the atomic volume and the positron lifetime of the elements of the periodic table. The differences between the BN, LDA and GGA schemes of calculations are pointed out too. (orig.)

  17. Characterisation of different polymorphs of tris(8-hydroxyquinolinatoaluminium(III using solid-state NMR and DFT calculations

    Directory of Open Access Journals (Sweden)

    Periasamy N

    2009-11-01

    Full Text Available Abstract Background Organic light emitting devices (OLED are becoming important and characterisation of them, in terms of structure, charge distribution, and intermolecular interactions, is important. Tris(8-hydroxyquinolinato-aluminium(III, known as Alq3, an organomettalic complex has become a reference material of great importance in OLED. It is important to elucidate the structural details of Alq3 in its various isomeric and solvated forms. Solid-state nuclear magnetic resonance (NMR is a useful tool for this which can also complement the information obtained with X-ray diffraction studies. Results We report here 27Al one-dimensional (1D and two-dimensional (2D multiple-quantum magic-angle spinning (MQMAS NMR studies of the meridional (α-phase and the facial (δ-phase isomeric forms of Alq3. Quadrupolar parameters are estimated from the 1D spectra under MAS and anisotropic slices of the 2D spectra and also calculated using DFT (density functional theory quantum-chemical calculations. We have also studied solvated phase of Alq3 containing ethanol in its lattice. We show that both the XRD patterns and the quadrupolar parameters of the solvated phase are different from both the α-phase and the δ-phase, although the fluorescence emission shows no substantial difference between the α-phase and the solvated phase. Moreover, we have shown that after the removal of ethanol from the matrix the solvated Alq3 has similar XRD patterns and quadrupolar parameters to that of the α-phase. Conclusion The 2D MQMAS experiments have shown that all the different modifications of Alq3 have 27Al in single unique crystallographic site. The quadrupolar parameters predicted using the DFT calculation under the isodensity polarisable continuum model resemble closely the experimentally obtained values. The solvated phase of Alq3 containing ethanol has structural difference from the α-phase of Alq3 (containing meridional isomer from the solid-state NMR studies

  18. Characterisation of different polymorphs of tris(8-hydroxyquinolinato)aluminium(III) using solid-state NMR and DFT calculations.

    Science.gov (United States)

    Goswami, Mithun; Nayak, Pabitra K; Periasamy, N; Madhu, P K

    2009-11-09

    Organic light emitting devices (OLED) are becoming important and characterisation of them, in terms of structure, charge distribution, and intermolecular interactions, is important. Tris(8-hydroxyquinolinato)-aluminium(III), known as Alq3, an organomettalic complex has become a reference material of great importance in OLED. It is important to elucidate the structural details of Alq3 in its various isomeric and solvated forms. Solid-state nuclear magnetic resonance (NMR) is a useful tool for this which can also complement the information obtained with X-ray diffraction studies. We report here 27Al one-dimensional (1D) and two-dimensional (2D) multiple-quantum magic-angle spinning (MQMAS) NMR studies of the meridional (alpha-phase) and the facial (delta-phase) isomeric forms of Alq3. Quadrupolar parameters are estimated from the 1D spectra under MAS and anisotropic slices of the 2D spectra and also calculated using DFT (density functional theory) quantum-chemical calculations. We have also studied solvated phase of Alq3 containing ethanol in its lattice. We show that both the XRD patterns and the quadrupolar parameters of the solvated phase are different from both the alpha-phase and the delta-phase, although the fluorescence emission shows no substantial difference between the alpha-phase and the solvated phase. Moreover, we have shown that after the removal of ethanol from the matrix the solvated Alq3 has similar XRD patterns and quadrupolar parameters to that of the alpha-phase. The 2D MQMAS experiments have shown that all the different modifications of Alq3 have 27Al in single unique crystallographic site. The quadrupolar parameters predicted using the DFT calculation under the isodensity polarisable continuum model resemble closely the experimentally obtained values. The solvated phase of Alq3 containing ethanol has structural difference from the alpha-phase of Alq3 (containing meridional isomer) from the solid-state NMR studies. Solid-state NMR can hence be

  19. 13C GIAO DFT calculation as a tool for configuration prediction of N-O group in saturated heterocyclic N-oxides

    Czech Academy of Sciences Publication Activity Database

    Pohl, Radek; Potmischil, F.; Dračínský, Martin; Vaněk, Václav; Slavětínská, Lenka; Buděšínský, Miloš

    2012-01-01

    Roč. 50, č. 6 (2012), s. 415-423 ISSN 0749-1581 R&D Projects: GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * 13C * 1H * saturated heterocyclic N-oxides * chemical shift calculations * DFT Subject RIV: CC - Organic Chemistry Impact factor: 1.528, year: 2012

  20. To address surface reaction network complexity using scaling relations machine learning and DFT calculations

    International Nuclear Information System (INIS)

    Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

    2017-01-01

    Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

  1. Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca- and Fe-doped MgO(001) surface basic sites.

    Science.gov (United States)

    Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

    2012-08-02

    The electronic properties of undoped and Ca- or Fe-doped MgO(001) surfaces, as well as their propensity toward atmospheric acidic gas (CO2, SO2, and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, O(surf), using periodic density functional theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the O(surf) sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe-doped MgO(001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca-doped MgO(001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces.

  2. Toward Reproducing Sequence Trends in Phosphorus Chemical Shifts for Nucleic Acids by MD/DFT Calculations

    Czech Academy of Sciences Publication Activity Database

    Přecechtělová, J.; Munzarová, M. L.; Vaara, J.; Novotný, J.; Dračínský, Martin; Sklenář, V.

    2013-01-01

    Roč. 9, č. 3 (2013), s. 1641-1656 ISSN 1549-9618 Grant - others:GA MŠk(CZ) LM2010005; GA MŠk(CZ) LC06030 Program:LC Institutional support: RVO:61388963 Keywords : density-funtional calculations * molecular-dynamics simulations * phosphate group * B-DNA Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.310, year: 2013

  3. 15 CFR 325.4 - Calculating time periods.

    Science.gov (United States)

    2010-01-01

    ... 15 Commerce and Foreign Trade 2 2010-01-01 2010-01-01 false Calculating time periods. 325.4 Section 325.4 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) INTERNATIONAL TRADE ADMINISTRATION, DEPARTMENT OF COMMERCE MISCELLANEOUS REGULATIONS EXPORT TRADE CERTIFICATES...

  4. Spectral studies of 2-pyrazoline derivatives: structural elucidation through single crystal XRD and DFT calculations.

    Science.gov (United States)

    Chinnaraja, D; Rajalakshmi, R; Srinivasan, T; Velmurugan, D; Jayabharathi, J

    2014-04-24

    A series of biologically active N-thiocarbamoyl pyrazoline derivatives have been synthesized using anhydrous potassium carbonate as the catalyst. All the synthesized compounds were characterized by FT-IR, (1)H NMR, (13)C NMR spectral studies, LCMS, CHN Analysis and X-ray diffraction analysis (compound 7). In order to supplement the XRD parameters, molecular modelling was carried out by Gaussian 03W. From the optimized structure, the energy, dipolemoment and HOMO-LUMO energies of all the systems were calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Combined hybrid functional and DFT+U calculations for metal chalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Aras, Mehmet; Kılıç, Çetin, E-mail: cetin-kilic@gyte.edu.tr [Department of Physics, Gebze Institute of Technology, Gebze, Kocaeli 41400 (Turkey)

    2014-07-28

    In the density-functional studies of materials with localized electronic states, the local/semilocal exchange-correlation functionals are often either combined with a Hubbard parameter U as in the LDA+U method or mixed with a fraction of exactly computed (Fock) exchange energy yielding a hybrid functional. Although some inaccuracies of the semilocal density approximations are thus fixed to a certain extent, the improvements are not sufficient to make the predictions agree with the experimental data. Here, we put forward the perspective that the hybrid functional scheme and the LDA+U method should be treated as complementary, and propose to combine the range-separated Heyd-Scuseria-Ernzerhof (HSE) hybrid functional with the Hubbard U. We thus present a variety of HSE+U calculations for a set of II-VI semiconductors, consisting of zinc and cadmium monochalcogenides, along with comparison to the experimental data. Our findings imply that an optimal value U{sup *} of the Hubbard parameter could be determined, which ensures that the HSE+U{sup *} calculation reproduces the experimental band gap. It is shown that an improved description not only of the electronic structure but also of the crystal structure and energetics is obtained by adding the U{sup *} term to the HSE functional, proving the utility of HSE+U{sup *} approach in modeling semiconductors with localized electronic states.

  6. High-pressure Raman spectra and DFT calculations of L-tyrosine hydrochloride crystal

    Science.gov (United States)

    dos Santos, C. A. A. S. S.; Carvalho, J. O.; da Silva Filho, J. G.; Rodrigues, J. L.; Lima, R. J. C.; Pinheiro, G. S.; Freire, P. T. C.; Façanha Filho, P. F.

    2018-02-01

    High-pressure Raman spectra of L-tyrosine hydrochloride crystal were obtained from 1.0 atm to 7.0 GPa in the 90-1800 cm-1 spectral region. At atmospheric pressure, the Raman spectrum was obtained in the 50-3200 cm-1 spectral range and the assignment of the normal modes based on density functional theory calculations was provided. We found good correspondence between the calculated and the observed intramolecular geometry parameters. This confirms the correct assignment of the normal modes, since it was crucial to understand the meaning of the changes observed in particular Raman active modes. Here we show that bands associated with internal modes undergo slight modifications during compression. However, an inversion of the relative intensity of bands around 125 cm-1 as well as a change of slope dω/dP from 1.0 to 1.5 GPa was understood as a conformational change involving a torsion of the L-tyrosine molecule. As a consequence, it is possible to conclude that the crystal remained in the same monoclinic structure in the 1 atm-7.0 GPa interval, although conformational change of the molecule was verified. A comparison of our results with other selected studies provided insights about the role of the amino acid side chain on the arrangement of hydrogen bonds. Finally, when the pressure was released back to 1 atm, the Raman spectrum was recovered and no hysteresis was observed.

  7. Thermodynamic characterization of lithium monosilicide (LiSi) by means of calorimetry and DFT-calculations

    Energy Technology Data Exchange (ETDEWEB)

    Taubert, Franziska; Seidel, Juergen; Huettl, Regina; Mertens, Florian [TU Bergakademie Freiberg (Germany). Inst. of Physical Chemistry; Schwalbe, Sebastian; Gruber, Thomas; Kortus, Jens [TU Bergakademie Freiberg (Germany). Inst. of Theoretical Chemistry; Janot, Raphael [Univ. de Picardie Jules Verne UMR 7314 CNRS, Amiens (France). Lab. de Reactivity et Chimie des Solides; Bobnar, Matej [Max-Planck-Institute for Chemical Physics of Solids, Dresden (Germany); Gumeniuk, Roman [TU Bergakademie Freiberg (Germany). Inst. of Experimental Physics

    2017-11-15

    In this work we summarize a symbiotic approach to combine experimental and theoretical investigations for the derivation of high quality thermodynamic data for the description of potential lithium ion battery materials. The methodology of this concept was demonstrated in detail by exploring and describing the properties of the lithium monosilicide phase LiSi. The procedures were also applied in a series of investigations to all major Li{sub x}Si{sub y}-phases which will be reviewed briefly. Regarding the LiSi phase, the measured and calculated isobaric heat capacity, which may enable further thermodynamic investigations (e.g. with CALPHAD method) of the phase diagram of the Li-Si-system is presented. The heat capacity of the stable phase LiSi was measured as a function of temperature in a range from (2 to 673) K and compared with corresponding ab-initio and molecular dynamic calculations resulting in values for absolute entropies. The heat of formation of the system was determined in an unconventional manner via hydrogenation experiments.

  8. Hindered rotational energy barriers of BH4- tetrahedra in β-Mg(BH4)2 from quasielastic neutron scattering and DFT calculations

    DEFF Research Database (Denmark)

    Blanchard, Didier; Maronsson, Jon Bergmann; Riktor, M.D.

    2012-01-01

    , around the 2-fold (C2) and 3-fold (C3) axes were observed at temperatures from 120 to 440 K. The experimentally obtained activation energies (EaC2 = 39 and 76 meV and EaC3 = 214 meV) and mean residence times between reorientational jumps are comparable with the energy barriers obtained from DFT......In this work, hindered rotations of the BH4- tetrahedra in Mg(BH4)2 were studied by quasielastic neutron scattering, using two instruments with different energy resolution, in combination with density functional theory (DFT) calculations. Two thermally activated reorientations of the BH4- units...... calculations. A linear dependency of the energy barriers for rotations around the C2 axis parallel to the Mg-Mg axis with the distance between these two axes was revealed by the DFT calculations. At the lowest temperature (120 K) only 15% of the BH4- units undergo rotational motion and from comparison with DFT...

  9. A periodic mixed gaussians-plane waves DFT study on simple thiols on Au(111): adsorbate species, surface reconstruction, and thiols functionalization.

    Science.gov (United States)

    Rajaraman, Gopalan; Caneschi, Andrea; Gatteschi, Dante; Totti, Federico

    2011-03-07

    Here we present DFT calculations based on a periodic mixed gaussians/plane waves approach to study the energetics, structure, bonding of SAMs of simple thiols on Au(111). Several open issues such as structure, bonding and the nature of adsorbate are taken into account. We started with methyl thiols (MeSH) on Au(111) to establish the nature of the adsorbate. We have considered several structural models embracing the reconstructed surface scenario along with the MeS˙-Au(ad)-MeS˙ type motif put forward in recent years. Our calculations suggest a clear preference for the homolytic cleavage of the S-H bond leading to a stable MeS˙ on a gold surface. In agreement with the recent literature studies, the reconstructed models of the MeS˙ species are found to be energetically preferred over unreconstructed models. Besides, our calculations reveal that the model with 1:2 Au(ad)/thiols ratio, i.e. MeS˙-Au(ad)-MeS˙, is energetically preferred compared to the clean and 1:1 ratio models, in agreement with the experimental and theoretical evidences. We have also performed Molecular Orbital/Natural Bond Orbital, MO/NBO, analysis to understand the electronic structure and bonding in different structural motifs and many useful insights have been gained. Finally, the studies have then been extended to alkyl thiols of the RSR' (R, R' = Me, Et and Ph) type and here our calculations again reveal a preference for the RS˙ type species adsorption for clean as well as for reconstructed 1:2 Au(ad)/thiols ratio models.

  10. 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.

  11. 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.

  12. Structural determination of stable MoOx monolayers on O/Cu3Au(1 0 0): DFT calculations

    International Nuclear Information System (INIS)

    Valadares, George C.S.; Mendes, F.M.T.; Dionízio Moreira, M.; Leitão, A.A.; Niehus, H.

    2012-01-01

    Highlights: ► Molybdenum oxide is widely used in catalysis in the chemical industry. ► Recently, ultra-thin (monolayer) films of MoO x have been produced on top of O-Cu 3 Au substrates. ► XPS measurements suggest an unusual +5 charge state of the Mo cation. ► Seeking for a low-energy structure with good match to the experimental STM and XPS. ► Bader charges indicate indeed an intermediate charge state as compared to the more common Mo +4 O 2 and Mo +6 O 3 bulk oxides. -- Abstract: Using ab initio calculations based on density functional theory (DFT), we propose a geometrical structure for MoO x monolayers recently grown on O/Cu 3 Au(1 0 0) substrates. The proposed structure reproduces the p(2 × 2) symmetry found by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED), as well as the intermediate oxidation state between Mo(IV) and Mo(VI) identified by X-ray photoelectron spectroscopy (XPS). Simulated STM images assign the bright spots in the experimental images to oxygen 2p states.

  13. Structure of Selected Derivates of p-Hydroxy Cynamonic Acid According to 13C CP MAS NMR and DFT Calculation

    International Nuclear Information System (INIS)

    Pisklak, D.M.; Wawer, I.; Tkaczyk, M.

    2005-01-01

    Derivatives of p-hydroxy cynamonic acid are widely occurring in fruits, vegetables, tea and coffee. They exhibit strong antioxidant activity due to the presence of phenolic group. Epidemiological, biological and biochemical data support health beneficial role of this group of compounds and anticarcinogenic, antimutagenic and antiinflamatory effects have been reported. The most common caffeic acid contributes significantly to the total polyphenol intake and has been suggested to play a role in the apparent association between the regular consumption of polyphenol-rich food and beverages, and the prevetion of inflammatory and proliferative diseases. 13 C MAS NMR spectra were recorded on a BRUKER DSX 400 spectrometer at 400,13. Powder samples were spun in a 4 mm rotor at 10 kHz ( 13 C). Signals were assigned:- By comparison with solution spectra; - Using dipolar dephasing and variable contact time experiments; - Confirmed by DFT calculations of shielding constants. The differences in chemical shifts between solution and solid state spectra are due to the formation of intramolecular and intermolecular hydrogen bonds, including C-OH...OC within cyclic dimers. (author)

  14. 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.

  15. 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.

  16. 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.

  17. Fluoridonitrosyl complexes of technetium(I) and technetium(II). Synthesis, characterization, reactions, and DFT calculations.

    Science.gov (United States)

    Balasekaran, Samundeeswari Mariappan; Spandl, Johann; Hagenbach, Adelheid; Köhler, Klaus; Drees, Markus; Abram, Ulrich

    2014-05-19

    A mixture of [Tc(NO)F5](2-) and [Tc(NO)(NH3)4F](+) is formed during the reaction of pertechnetate with acetohydroxamic acid (Haha) in aqueous HF. The blue pentafluoridonitrosyltechnetate(II) has been isolated in crystalline form as potassium and rubidium salts, while the orange-red ammine complex crystallizes as bifluoride or PF6(-) salts. Reactions of [Tc(NO)F5](2-) salts with HCl give the corresponding [Tc(NO)Cl4/5](-/2-) complexes, while reflux in neat pyridine (py) results in the formation of the technetium(I) cation [Tc(NO)(py)4F](+), which can be crystallized as hexafluoridophosphate. The same compound can be synthesized directly from pertechnetate, Haha, HF, and py or by a ligand-exchange procedure starting from [Tc(NO)(NH3)4F](HF2). The technetium(I) cation [Tc(NO)(NH3)4F](+) can be oxidized electrochemically or by the reaction with Ce(SO4)2 to give the corresponding Tc(II) compound [Tc(NO)(NH3)4F](2+). The fluorido ligand in [Tc(NO)(NH3)4F](+) can be replaced by CF3COO(-), leaving the "[Tc(NO)(NH3)4](2+) core" untouched. The experimental results are confirmed by density functional theory calculations on [Tc(NO)F5](2-), [Tc(NO)(py)4F](+), [Tc(NO)(NH3)4F](+), and [Tc(NO)(NH3)4F](2+).

  18. Effect of transition metal-doped Ni(211) for CO dissociation: Insights from DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Kuiwei; Zhang, Minhua [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China)

    2017-03-31

    Highlights: • Doping the step edge of Ni(211) with Fe or Ru observably enhances CO dissociation. • Rh doping is unfavorable for CO activation both kinetically and thermodynamically. • Two neat linear relations are proposed besides the Brønsted–Evans–Polanyi relation. • The differences of CO adsorption are rationalized via the Blyholder model. - Abstract: Density functional theory slab calculations were performed to investigate the adsorption and dissociation of CO over pure and M-doped Ni(211) (M = Fe, Co, Ru and Rh) with the aim to elucidate the effect of transition metal doping for CO activation. Doping the step edge of Ni(211) with Fe, Co and Ru is found to enhance the binding of CO in the initial state (IS) (in the sequence by the improvement degree: Fe > Ru > Co) as well as the co-adsorption of C and O in the final state (FS) (Ru > Fe > Co). In contrast, Rh doping is unfavorable both in the IS and in the FS. Analysis of the overall potential energy surfaces (PES) suggests CO dissociation is facilitated by Fe, Ru and Co doping both kinetically and thermodynamically, wherein Fe and Ru behave extraordinary. Interestingly, Fe substitute is slightly superior to Ru in kinetics whereas the contrary is the case in thermodynamics. Rh doping elevates the energy height from 0.97 eV on Ni(211) to 1.32 eV and releases 0.39 eV less heat relative to Ni(211), again manifesting a negative effect. Besides the classical Brønsted–Evans–Polanyi relationship, we put forward another two neat linear relations, which can well describe the feature of CO dissociation. The differences of CO adsorption and activation in the IS over pure and doped Ni(211) surfaces are rationalized via electronic structure analysis. The findings presented herein are expected to provide theoretical guidance for catalyst design and optimization in relevant processes.

  19. Adsorption of SO{sub 2} on Li atoms deposited on MgO (1 0 0) surface: DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Eid, Kh.M., E-mail: Kheid98@hotmail.com [Physics Department, Faculty of Education, Ain Shams University, Cairo 11757 (Egypt); Ammar, H.Y. [Department of Physics, Faculty of Science, Najran University, Najran 1988 (Saudi Arabia)

    2011-05-01

    The adsorption of sulfur dioxide molecule (SO{sub 2}) on Li atom deposited on the surfaces of metal oxide MgO (1 0 0) on both anionic and defect (F{sub s}-center) sites located on various geometrical defects (terrace, edge and corner) has been studied using density functional theory (DFT) in combination with embedded cluster model. The adsorption energy (E{sub ads}) of SO{sub 2} molecule (S-atom down as well as O-atom down) in different positions on both of O{sup -2} and F{sub s} sites is considered. The spin density (SD) distribution due to the presence of Li atom is discussed. The geometrical optimizations have been done for the additive materials and MgO substrate surfaces (terrace, edge and corner). The oxygen vacancy formation energies have been evaluated for MgO substrate surfaces. The ionization potential (IP) for defect free and defect containing of the MgO surfaces has been calculated. The adsorption properties of SO{sub 2} are analyzed in terms of the E{sub ads}, the electron donation (basicity), the elongation of S-O bond length and the atomic charges on adsorbed materials. The presence of the Li atom increases the catalytic effect of the anionic O{sup -2} site of MgO substrate surfaces (converted from physisorption to chemisorption). On the other hand, the presence of the Li atom decreases the catalytic effect of the F{sub s}-site of MgO substrate surfaces. Generally, the SO{sub 2} molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F{sub s}-center.

  20. Synthesis, spectroscopic characterization, biological studies and DFT calculations on some transition metal complexes of NO donor ligand

    Science.gov (United States)

    Zordok, W. A.; Sadeek, S. A.

    2018-04-01

    Seven new complexes of2-oxo-4,6-diphenyl-1,2-dihyropyridine-3-carbonitrile (L) with Fe(III), Co(II), Cu(II), Zn(II), Y(III), Zr(IV) and La(III) were synthesized. The isolated solid compounds were elucidated from micro analytical, IR, electronic, mass, 1H NMR, magnetic susceptibility measurements and TG/DTG, DTA analyses. The intensity of ν(Ctbnd N) was changed to strong and shifted to around 2200 cm-1. Also, the ν(Cdbnd O) was shifted to higher frequency value (1644 cm-1). The spectra of the complexes indicate that the free ligand is coordinated to the metal ions via nitrogen of carbonitrile group and oxygen of keto group. From DFT calculations the Cu(II) and Fe(III) complexes behave as regular octahedral, while other complexes are distorted octahedral. The value of energy gap of the free ligand (ΔE = 0.3343 eV) is greater than all new complexes, so they are more reactive than free ligand, also the Fe(III) complex (ΔE = 0.0985 eV) is the most reactive complex, while Cu(II) complex (ΔE = 0.3219 eV) is the least reactive complex. The LMCT in case of Zr(IV) complex was resulted from transitions from HOMO-2 (62%), HOMO-1 (16%)and HOMO (25%), while the d-d transition in Fe(III) complex was resulted from HOMO-1(30%), HOMO-2(62%) and HOMO(30%). Also, the metal complexes exhibit antibacterial activity for Gram-positive and Gram-negative and antifungal activity. The Y(III) and Cu(II) complexes are highly significant for Escherichia coli and salmonella typhimurium.

  1. Oligothiophene-based colorimetric and ratiometric fluorescence dual-channel cyanide chemosensor: Sensing ability, TD-DFT calculations and its application as an efficient solid state sensor

    Science.gov (United States)

    Lan, Linxin; Li, Tianduo; Wei, Tao; Pang, He; Sun, Tao; Wang, Enhua; Liu, Haixia; Niu, Qingfen

    2018-03-01

    An oligothiophene-based colorimetric and ratiometric fluorescence dual-channel cyanide chemosensor 3 T-2CN was reported. Sensor 3 T-2CN showed both naked-eye recognition and ratiometric fluorescence response for CN- with an excellent selectivity and high sensitivity. The sensing mechanism based on the nucleophilic attack of CN- on the vinyl Cdbnd C bond has been successfully confirmed by the optical measurements, 1H NMR titration, FT-IR spectra as well as the DFT/TD-DFT calculations. Moreover, the detection limit was calculated to be 0.19 μM, which is much lower than the maximum permission concentration in drinking water (1.9 μM). Importantly, test strips (filter paper and TLC plates) containing 3 T-2CN were fabricated, which could act as a practical and efficient solid state optical sensor for CN- in field measurements.

  2. Calorimetric, FTIR and 1H NMR measurements in combination with DFT calculations for monitoring solid-state changes of dynamics of sibutramine hydrochloride.

    Science.gov (United States)

    Pajzderska, Aleksandra; Chudoba, Dorota M; Mielcarek, Jadwiga; Wąsicki, Jan

    2012-10-01

    Two forms of sibutramine hydrochloride, monohydrate and anhydrous, have been investigated by calorimetric methods, Fourier transform infrared (FTIR) absorption and (1) H nuclear magnetic resonance (NMR) measurements as well as by density functional theory (DFT) of vibrational frequencies and infrared intensities, calculations of steric hindrances and Monte Carlo simulations. The results of FTIR spectra combined with DFT calculations permitted identification of the bands corresponding to the dynamics and vibrations of water molecules. NMR study and Monte Carlo simulations revealed the occurrence of reorientation jumps of the methyl groups in sibutramine cation and also revealed that the reorientation of isopropyl group is possible only in sibutramine monohydrate hydrochloride. The hydration of sibutramine hydrochloride causes a change in the conformation of sibutramine cation. Copyright © 2012 Wiley-Liss, Inc.

  3. 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.

  4. Synthesis, Crystal Structures, and DFT Calculations of Three New Cyano(phenylsulfonylindoles and a Key Synthetic Precursor Compound

    Directory of Open Access Journals (Sweden)

    William L. Montgomery

    2015-09-01

    Full Text Available Three cyano-1-(phenylsulfonylindole derivatives, 3-cyano-1-(phenylsulfonyl indole, (I, 2-cyano-1-(phenylsulfonylindole, (II, and 2,3-dicyano-1-(phenylsulfonyl indole, (III, and a key synthetic precursor 1-(phenylsulfonyl-1-(1,1-dimethylethyl indole-3-carboxamide, (IV, have been synthesized and their structures determined by single crystal X-ray crystallography. (I, C15H10N2O2S, is orthorhombic with space group P 212121 and cell constants: a = 4.9459(3 Å, b = 10.5401(7 Å, c = 25.0813(14 Å, V = 1307.50(14 Å3 and Z = 4. (II, C15H10N2O2S, is monoclinic with space group C 2/c and cell constants: a = 18.062(2 Å, b = 11.293(2 Å, c = 15.922(3 Å, α = 90°, β = 124.49(2°, g = 90°, V = 2676.7 Å3 and Z = 8. (III, C16H9N3O2S, is triclinic with space group P-1 and cell constants: a = 8.1986(8 Å, b = 9.6381(11 Å, c = 9.8113(5 Å, α = 95.053(6°, β = 101.441(6°, g = 108.071(9°, V = 713.02(11 Å3 and Z = 2. (IV, C19H20N2O3S, is orthorhombic with space group P ccn and cell constants: a = 13.7605(8 Å, b = 27.3177(14 Å, c = 9.7584(6 Å, α = 90°, β = 90°, g =90°, V = 3668.2(4 Å3 and Z = 8. All four compounds have the same indole nitrogen phenylsulfonyl substituent and (I, (II, and (III are nitrile derivatives. (IV is a tert-butylamide. In the crystals, the dihedral angle between the mean planes of the indole and phenylsulfonyl groups are 85.4(2° (I, 87.2(7° (II, 75.1(7° (III, and 88.6(2° (IV, respectively. Additionally, DFT geometry-optimized molecular orbital calculations were performed and frontier molecular orbitals of each compound are displayed. Correlation between the calculated molecular orbital energies (eV for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound has been proposed.

  5. Calculation of period processing solution syrup in vacuum apparatus

    Directory of Open Access Journals (Sweden)

    A. A. Slavyanskii

    2016-01-01

    Full Text Available Important and crucial element in the management of the technological flow of production of sugar product standards is the period of time the enrichment of massecuite, since its neutralization in the process of crystal formation in vacuum apparatus, excess sugar solution. Although currently proposed and implemented in the industry, including as a front-end accompany the process, a number of ways in the real world sugar production in many cases have to resort to the services of an experienced operator. It is obvious that in any case it is necessary to have a surround-dependent glucose solution data on time for the excess sugar solution into the vacuum apparatus. With regard to the period of the enrichment of depleted sucrose solution are entered into this substance excess sucrose solution, it should be noted that this problem is theoretically still insufficiently developed. It is obvious that for practical purposes it is desirable to have a simple and convenient for engineering calculation of sugar processing time dependencies of the specified volume of water from the operating parameters of the process (the required concentration of sucrose, temperature of the solution stirring. The problem is the quantitative analysis of sucrose crystallization in vacuum apparatus, including the timing of enrichment solution to the excess syrup, period of time processing massecuite total this apparatus has been investigated in many works. However, due to its importance to the task of obtaining commercial sugar high standards this issue required further in-depth examination. In the article to support the enrichment process solution sucrose due to neutralize this solvent system in vacuum apparatus, from the standpoint of diffusion theory provides a more reasonable compared to known so far, quantitative analysis of this process. Where as sucrose crystals team are considering a system of balls, uniformly distributed in vacuum apparatus. On the basis of the solution

  6. 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.

  7. Geometrical correction for the inter- and intramolecular basis set superposition error in periodic density functional theory calculations.

    Science.gov (United States)

    Brandenburg, Jan Gerit; Alessio, Maristella; Civalleri, Bartolomeo; Peintinger, Michael F; Bredow, Thomas; Grimme, Stefan

    2013-09-26

    We extend the previously developed geometrical correction for the inter- and intramolecular basis set superposition error (gCP) to periodic density functional theory (DFT) calculations. We report gCP results compared to those from the standard Boys-Bernardi counterpoise correction scheme and large basis set calculations. The applicability of the method to molecular crystals as the main target is tested for the benchmark set X23. It consists of 23 noncovalently bound crystals as introduced by Johnson et al. (J. Chem. Phys. 2012, 137, 054103) and refined by Tkatchenko et al. (J. Chem. Phys. 2013, 139, 024705). In order to accurately describe long-range electron correlation effects, we use the standard atom-pairwise dispersion correction scheme DFT-D3. We show that a combination of DFT energies with small atom-centered basis sets, the D3 dispersion correction, and the gCP correction can accurately describe van der Waals and hydrogen-bonded crystals. Mean absolute deviations of the X23 sublimation energies can be reduced by more than 70% and 80% for the standard functionals PBE and B3LYP, respectively, to small residual mean absolute deviations of about 2 kcal/mol (corresponding to 13% of the average sublimation energy). As a further test, we compute the interlayer interaction of graphite for varying distances and obtain a good equilibrium distance and interaction energy of 6.75 Å and -43.0 meV/atom at the PBE-D3-gCP/SVP level. We fit the gCP scheme for a recently developed pob-TZVP solid-state basis set and obtain reasonable results for the X23 benchmark set and the potential energy curve for water adsorption on a nickel (110) surface.

  8. VLSI Architectures for Computing DFT's

    Science.gov (United States)

    Truong, T. K.; Chang, J. J.; Hsu, I. S.; Reed, I. S.; Pei, D. Y.

    1986-01-01

    Simplifications result from use of residue Fermat number systems. System of finite arithmetic over residue Fermat number systems enables calculation of discrete Fourier transform (DFT) of series of complex numbers with reduced number of multiplications. Computer architectures based on approach suitable for design of very-large-scale integrated (VLSI) circuits for computing DFT's. General approach not limited to DFT's; Applicable to decoding of error-correcting codes and other transform calculations. System readily implemented in VLSI.

  9. 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.

  10. Sodium and potassium salts of dichloroisocyanuric acid and their hydrates as antimicrobials agents studied by 35Cl-NQR spectroscopy and DFT calculations

    International Nuclear Information System (INIS)

    Walczak, A.; Brycki, B.; Kaczmarek, M.; Poleshchuk, O.Kh.; Ostafin, M.; Nogaj, B.

    2006-01-01

    The electronic structure of dichloroisocyanuric acid derivatives was analysed by 35 Cl-NQR spectroscopy and DFT calculations. Here we concentrate our attention on three different factors: type of metallic substituent (sodium and potassium), temperature of the sample (liquid nitrogen and room) and degree of hydration (an amount of water molecules attached to analysed compounds). In particular, all the variations in 35 Cl-NQR frequencies upon hydration of salts containing sodium and potassium ions are explained as a consequence of H-bonds formation and accompanied effects of charge redistribution. Our studies can be useful in searching for the derivatives of dichloroisocyanuric acid revealing higher antimicrobial activity

  11. 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.

  12. Electrostatic frequency maps for amide-I mode of β-peptide: Comparison of molecular mechanics force field and DFT calculations

    Science.gov (United States)

    Cai, Kaicong; Zheng, Xuan; Du, Fenfen

    2017-08-01

    The spectroscopy of amide-I vibrations has been widely utilized for the understanding of dynamical structure of polypeptides. For the modeling of amide-I spectra, two frequency maps were built for β-peptide analogue (N-ethylpropionamide, NEPA) in a number of solvents within different schemes (molecular mechanics force field based, GM map; DFT calculation based, GD map), respectively. The electrostatic potentials on the amide unit that originated from solvents and peptide backbone were correlated to the amide-I frequency shift from gas phase to solution phase during map parameterization. GM map is easier to construct with negligible computational cost since the frequency calculations for the samples are purely based on force field, while GD map utilizes sophisticated DFT calculations on the representative solute-solvent clusters and brings insight into the electronic structures of solvated NEPA and its chemical environments. The results show that the maps' predicted amide-I frequencies present solvation environmental sensitivities and exhibit their specific characters with respect to the map protocols, and the obtained vibrational parameters are in satisfactory agreement with experimental amide-I spectra of NEPA in solution phase. Although different theoretical schemes based maps have their advantages and disadvantages, the present maps show their potentials in interpreting the amide-I spectra for β-peptides, respectively.

  13. Synthesis, molecular docking, DFT calculations and cytotoxicity activity of benzo[g]quinazoline derivatives in choline chloride-urea

    Science.gov (United States)

    Lakshmanan, Sivalingam; Govindaraj, Dharman; Ramalakshmi, Narayanan; Antony, S. Arul

    2017-12-01

    Green and highly efficient one-pot three component approach for the synthesis of benzo[g]quinazoline derivatives (6a-g) using Choline chloride-urea (DES). Synthesized compounds 6b and 6g showed the most potent biological activity against A549 lung cancer cell line. Docking simulation was performed to position compounds 6b and 6g showed the greater affinity for anaplastic lymphoma kinase (ALK) receptor. Quantum chemical studies were carried out on these compounds to understand the structural features essential for activity using DFT/6-31G level of theory.

  14. Rose-like I-doped Bi_2O_2CO_3 microspheres with enhanced visible light response: DFT calculation, synthesis and photocatalytic performance

    International Nuclear Information System (INIS)

    Zai, Jiantao; Cao, Fenglei; Liang, Na; Yu, Ke; Tian, Yuan; Sun, Huai; Qian, Xuefeng

    2017-01-01

    Highlights: • DFT reveals I"− can partially substitute CO_3"2"−to narrow the bandgap of Bi_2O_2CO_3. • Sodium citrate play a key role on the formation of rose-like I-doped Bi_2O_2CO_3. • Rose-like I-doped Bi_2O_2CO_3 show enhanced visible light response. • The catalyst has enhanced photocatalytic activity to organic and Cr(VI) pollutes. - Abstract: Based on the crystal structure and the DFT calculation of Bi_2O_2CO_3, I"− can partly replace the CO_3"2"−in Bi_2O_2CO_3 to narrow its bandgap and to enhance its visible light absorption. With this in mind, rose-like I-doped Bi_2O_2CO_3 microspheres were prepared via a hydrothermal process. This method can also be extended to synthesize rose-like Cl- or Br-doped Bi_2O_2CO_3 microspheres. Photoelectrochemical test supports the DFT calculation result that I- doping narrows the bandgap of Bi_2O_2CO_3 by forming two intermediate levels in its forbidden band. Further study reveals that I-doped Bi_2O_2CO_3 microspheres with optimized composition exhibit the best photocatalytic activity. Rhodamine B can be completely degraded within 6 min and about 90% of Cr(VI) can be reduced after 25 min under the irradiation of visible light (λ > 400 nm).

  15. Anisotropic lattice thermal expansion of PbFeBO4: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

    International Nuclear Information System (INIS)

    Murshed, M. Mangir; Mendive, Cecilia B.; Curti, Mariano; Nénert, Gwilherm; Kalita, Patricia E.; Lipinska, Kris; Cornelius, Andrew L.; Huq, Ashfia; Gesing, Thorsten M.

    2014-01-01

    Highlights: • Mullite-type PbFeBO 4 shows uni-axial negative coefficient of thermal expansion. • Anisotropic thermal expansion of the metric parameters was modeled using modified Grüneisen approximation. • The model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy. • DFT calculation, temperature- and pressure-dependent Raman spectra help understand the phonon decay and associated anharmonicity. - Abstract: The lattice thermal expansion of mullite-type PbFeBO 4 is presented in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. The unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequencies of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO 4 , FeO 6 and BO 3 polyhedra as a function of temperature

  16. Expedient and click synthesis, spectroscopic characterizations and DFT calculations of novel 1,5-bis(N-substituted 1,2,3‒triazole) benzodiazepinedione scaffolds

    Science.gov (United States)

    Paghandeh, Hossein; Saeidian, Hamid

    2018-04-01

    A practically reliable procedure for synthesis of new 1,5-bis(N-substituted 1,2,3‒triazole) benzodiazepinedione derivatives was reported by sequential amidation, propargylation and a click azide‒alkyne [3 + 2] cycloaddition reaction in a one pot fashion. The desired products were characterized by CHN analysis, 1H and 13C NMR and ESI-MS spectroscopy. Short reaction time, good yields (55-91%), mild reaction conditions and easily available and less expensive starting materials are advantages of this protocol. Natural bond orbital charge distribution and HOMO-LUMO analysis of the characterized structure of 4e have been also calculated by density functional theory (DFT) calculations. The Li+ and Na+ ion affinities of 4e have been also investigated by DFT studies to find the applicability of these products as ligand in coordination chemistry. Sodium ion affinity of 4e was determined as 60 kJ mol-1 is less than its lithium ion affinity, indicating that the lithiation of 4e is more exothermic than the sodiation.

  17. Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile-ketenimine equilibria.

    Science.gov (United States)

    Giussi, Juan M; Gastaca, Belen; Albesa, Alberto; Cortizo, M Susana; Allegretti, Patricia E

    2011-02-01

    The study of tautomerics equilibria is really important because the reactivity of each compound with tautomeric capacity can be determined from the proportion of each tautomer. In the present work the tautomeric equilibria in some γ,δ-unsaturated β-hydroxynitriles and γ,δ-unsaturated β-ketonitriles were studied. The first family of compounds presents two possible theoretical tautomers, nitrile and ketenimine, while the second one presents four possible theoretical tautomers, keto-nitrile, enol (E and Z)-nitrile and keto-ketenimine. The equilibrium in gas phase was studied by gas chromatography-mass spectrometry (GC-MS). Tautomerization enthalpies were calculated by this methodology, and results were compared with those obtained by density functional theory (DFT) calculations, observing a good agreement between them. Nitrile tautomers were favored within the first family of compounds, while keto-nitrile tautomers were favored in the second family. Copyright © 2010 Elsevier B.V. All rights reserved.

  18. 13C CP MAS NMR and GIAO-CHF/DFT calculations of flavonoids: Morin, kaempferol, tricin, genistein, formononetin and 3,7-dihydroxyflavone

    Science.gov (United States)

    Zielińska, Agnieszka; Paradowska, Katarzyna; Jakowski, Jacek; Wawer, Iwona

    2008-02-01

    13C CP MAS NMR spectra of the flavonoids: morin, kaempferol, 3,7-dihydroxyflavone, tricin and isoflavones: genistein and formononetin were recorded to characterize solid-state conformations. Intramolecular hydrogen bonds forming five-, six- and seven-membered rings are present in the two morin molecules in the crystals - their 13C resonances have been assigned with the aid of the calculated shielding constants. Linear relationships between the calculated shielding constants σDFT (ppm) and chemical shifts ( δCPMAS, ppm) were obtained for all studied compounds. Higher correlation coefficients suggest that the conformation with "clockwise" orientation of both OH groups is more probable in the solid 3,7-dihydroxyflavone, whereas in the solid formononetin the OH and OCH 3 substituents are directed "anticlockwise". The barrier to the rotation of phenyl ring B decreases in the order: morin (2'-OH, 3-OH) > kaempferol (3-OH) > tricin.

  19. Cluster model calculations of alpha decays across the periodic table

    International Nuclear Information System (INIS)

    Merchant, A.C.; Buck, B.

    1988-10-01

    The cluster model of Buck, Dover and Vary has been used to calculate partial widths for alpha decay from the ground states of all nuclei for which experimental measurements exist. The cluster-core potential is represented by a simple three-parameter form having fixed diffuseness, a radius which scales as A 1/3 and a depth which is adjusted to fit the Q-value of the particular decay. The calculations yield excellent agreement with the vast majority of the available data, and some typical examples are presented. (author) [pt

  20. Electronic structure and optical properties of Cs2HgCl4: DFT calculations and X-ray photoelectron spectroscopy measurements

    Science.gov (United States)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

    2016-10-01

    A high-quality single crystal of cesium mercury tetrabromide, Cs2HgCl4, was synthesized by using the vertical Bridgman-Stockbarger method and its electronic structure was studied from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectra were measured for both pristine and Ar+ ion-bombarded Cs2HgCl4 single crystal surfaces. The present XPS measurements indicate that the Cs2HgCl4 single crystal surface is sensitive with respect to Ar+ ion-bombardment: such a treatment changes substantially its elemental stoichiometry. With the aim of exploring total and partial densities of states within the valence band and conduction band regions of the Cs2HgCl4 compound, band-structure calculations based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method as incorporated within the WIEN2k package are performed. The calculations indicate that the Cl 3p states are the principal contributors in the upper portion of the valence band, while the Hg 5d and Cs 5p states dominate in its lower portion. In addition, the calculations allow for concluding that the unoccupied Cl p and Hg s states are the main contributors to the bottom of the conduction band. Furthermore, main optical characteristics of Cs2HgCl4, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity, are elucidated based on the DFT calculations.

  1. 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

  2. Amplitude calculation near a period-doubling bifurcation: An example

    DEFF Research Database (Denmark)

    Wiesenfeld, K.; Pedersen, Niels Falsig

    1987-01-01

    For the rf-driven Josephson junction, the dynamical behavior is studied near a period-doubling transition. The center-manifold theorem simplifies the problem and enables us to study only a first-order system, the parameters of which are expressed in terms of the Josephson-junction parameters....

  3. Characterizing the Solvated Structure of Photoexcited [Os(terpy2]2+ with X-ray Transient Absorption Spectroscopy and DFT Calculations

    Directory of Open Access Journals (Sweden)

    Xiaoyi Zhang

    2016-02-01

    Full Text Available Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of “red sensitizers” based on osmium(II polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy2]2+ (terpy: 2,2′:6′,2″-terpyridine solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN6]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT and the near-edge region of the X-ray spectra.

  4. 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.

  5. 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.

  6. The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations

    Science.gov (United States)

    Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata

    2018-01-01

    Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc)2, depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na+ cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na+ cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. [Figure not available: see fulltext.

  7. Accurate orbital-dependent correlation and exchange-correlation potentials from non-iterative ab initio dft calculations

    Science.gov (United States)

    Grabowski, Ireneusz; Lotrich, Victor

    2005-08-01

    A new approximate non-iterative procedure to obtain accurate correlation and exchange-correlation potentials of Kohn-Sham (KS) density functional theory (DFT) is presented. By carrying out only one step of the correlated optimized effective potential (OEP) iterations following the standard iterative exchange-only OEP, one can recover accurate correlation potentials corresponding to the orbital-dependent second-order many-body perturbation theory [MBPT(2)] energy functional that are hardly discernible from those obtained by the more expensive, fully iterative procedure. This new 'one-step' OEP-MBPT(2) algorithm reflects the non-iterative, perturbative algorithm of standard, canonical MBPT(2) of ab initio wave function theory, while it allows the correlation potentials to readjust and include the majority of the MBPT(2) correlation effect. It is also flexible in the treatment of exchange and the Hartree-Fock orbitals may be used in lieu of the exchange-only OEP orbitals, when the correlation or exchange-correlation potential is of interest.

  8. Combining density functional theory (DFT) and collision cross-section (CCS) calculations to analyze the gas-phase behaviour of small molecules and their protonation site isomers.

    Science.gov (United States)

    Boschmans, Jasper; Jacobs, Sam; Williams, Jonathan P; Palmer, Martin; Richardson, Keith; Giles, Kevin; Lapthorn, Cris; Herrebout, Wouter A; Lemière, Filip; Sobott, Frank

    2016-06-20

    Electrospray ion mobility-mass spectrometry (IM-MS) data show that for some small molecules, two (or even more) ions with identical sum formula and mass, but distinct drift times are observed. In spite of showing their own unique and characteristic fragmentation spectra in MS/MS, no configurational or constitutional isomers are found to be present in solution. Instead the observation and separation of such ions appears to be inherent to their gas-phase behaviour during ion mobility experiments. The origin of multiple drift times is thought to be the result of protonation site isomers ('protomers'). Although some important properties of protomers have been highlighted by other studies, correlating the experimental collision cross-sections (CCSs) with calculated values has proven to be a major difficulty. As a model, this study uses the pharmaceutical compound melphalan and a number of related molecules with alternative (gas-phase) protonation sites. Our study combines density functional theory (DFT) calculations with modified MobCal methods (e.g. nitrogen-based Trajectory Method algorithm) for the calculation of theoretical CCS values. Calculated structures can be linked to experimentally observed signals, and a strong correlation is found between the difference of the calculated dipole moments of the protomer pairs and their experimental CCS separation.

  9. Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

    Science.gov (United States)

    Avdeev, Vasilii I.; Bedilo, Alexander F.

    2018-03-01

    The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

  10. A real-time fluorescent sensor specific to Mg2+: crystallographic evidence, DFT calculation and its use for quantitative determination of magnesium in drinking water.

    Science.gov (United States)

    Men, Guangwen; Chen, Chunrong; Zhang, Shitong; Liang, Chunshuang; Wang, Ying; Deng, Mengyu; Shang, Hongxing; Yang, Bing; Jiang, Shimei

    2015-02-14

    An "off-the-shelf" fluorescence "turn-on" Mg(2+) chemosensor 3,5-dichlorosalicylaldehyde (BCSA) was rationally designed and developed. This proposed sensor works based on Mg(2+)-induced formation of the 2 : 1 BCSA-Mg(2+) complex. The coordination of BSCA to Mg(2+) increases its structural rigidity generating a chelation-enhanced fluorescence (CHEF) effect which was confirmed by single crystal XRD studies of the BSCA-Mg(2+) complex and TD/DFT calculations. This sensor exhibits high sensitivity and selectivity for the quantitative monitoring of Mg(2+) with a wide detection range (0-40 μM), a low detection limit (2.89 × 10(-7) mol L(-1)) and a short response time (sensor can be utilized to monitor Mg(2+) in real time within actual samples from drinking water.

  11. Benzothiazole analogues: Synthesis, characterization, MO calculations with PM6 and DFT, in silico studies and in vitro antimalarial as DHFR inhibitors and antimicrobial activities.

    Science.gov (United States)

    Thakkar, Sampark S; Thakor, Parth; Ray, Arabinda; Doshi, Hiren; Thakkar, Vasudev R

    2017-10-15

    Benzothiazole analogues are of interest due to their potential activity against malarial and microbial infections. In search of suitable antimicrobial and antimalarial agents, we report here the synthesis, characterization and biological activities of benzothiazole analogues (J 1-J 10). The molecules were characterized by IR, Mass, 1 H NMR, 13 C NMR and elemental analysis. The in vitro antimicrobial activity was investigated against pathogenic strains; the results were explained with the help of DFT and PM6 molecular orbital calculations. In vitro cytotoxicity and genotoxicity of the molecules were studied against S. pombe cells. In vitro antimalarial activity was studied. The active compounds J 1, J 2, J 3, J 5 and J 6 were further evaluated for enzyme inhibition efficacy against the receptor Pf-DHFR, computational and in vitro studies were carried out to examine their candidatures as lead dihydrofolate reductase inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. 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.

  13. Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.

    Science.gov (United States)

    Enemark, John H

    2017-10-10

    Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (P i ) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here. Errors in some of the previously proposed structures are corrected.

  14. Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations.

    Science.gov (United States)

    Mendt, Matthias; Barth, Benjamin; Hartmann, Martin; Pöppl, Andreas

    2017-12-14

    The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an 27 Al atom and all its relevant 14 N and 27 Al hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al 3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al 3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules.

  15. 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.

  16. Low-temperature binding of NO adsorbed on MIL-100(Al)—A case study for the application of high resolution pulsed EPR methods and DFT calculations

    Science.gov (United States)

    Mendt, Matthias; Barth, Benjamin; Hartmann, Martin; Pöppl, Andreas

    2017-12-01

    The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an 27Al atom and all its relevant 14N and 27Al hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules.

  17. Ruthenium(II) bipyridine complexes bearing new keto-enol azoimine ligands: synthesis, structure, electrochemistry and DFT calculations.

    Science.gov (United States)

    Al-Noaimi, Mousa; Awwadi, Firas F; Mansi, Ahmad; Abdel-Rahman, Obadah S; Hammoudeh, Ayman; Warad, Ismail

    2015-01-25

    The novel azoimine ligand, Ph-NH-N=C(COCH3)-NHPh(C≡CH) (H2L), was synthesized and its molecular structure was determined by X-ray crystallography. Catalytic hydration of the terminal acetylene of H2L in the presence of RuCl3·3H2O in ethanol at reflux temperature yielded a ketone (L1=Ph-N=N-C(COCH3)=N-Ph(COCH3) and an enol (L2=Ph-N=N-C(COCH3)=N-PhC(OH)=CH2) by Markovnikov addition of water. Two mixed-ligand ruthenium complexes having general formula, trans-[Ru(bpy)(Y)Cl2] (1-2) (where Y=L1 (1) and Y=L2 (2), bpy is 2.2'-bipyrdine) were achieved by the stepwise addition of equimolar amounts of (H2L) and bpy ligands to RuCl3·3H2O in absolute ethanol. Theses complexes were characterized by elemental analyses and spectroscopic (IR, UV-Vis, and NMR (1D (1)H NMR, (13)C NMR, (DEPT-135), (DEPT-90), 2D (1)H-(1)H and (13)C-(1)H correlation (HMQC) spectroscopy)). The two complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 604 mV vs. ferrocene/ferrocenium (Cp2Fe(0/+)) couple along with one electron ligand reduction at -1010 mV. The crystal structure of complex 1 showed that the bidentate ligand L1 coordinates to Ru(II) by the azo- and imine-nitrogen donor atoms. The complex adopts a distorted trans octahedral coordination geometry of chloride ligands. The electronic spectra of 1 and 1+ in dichloromethane have been modeled by time-dependent density functional theory (TD-DFT). Copyright © 2014 Elsevier B.V. All rights reserved.

  18. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    Science.gov (United States)

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  19. DFT calculation for elastic constants of orthorhombic structure within WIEN2K code: A new package (ortho-elastic)

    International Nuclear Information System (INIS)

    Reshak, Ali H.; Jamal, Morteza

    2012-01-01

    Highlights: ► A new package for calculating elastic constants of orthorhombic structure is released. ► The package called ortho-elastic. ► It is compatible with [FP-(L)APW+lo] method implemented in WIEN2k code. ► Several orthorhombic structure compounds were used to test the new package. ► Elastic constants calculated using this package show good agreement with experiment. - Abstract: A new package for calculating the elastic constants of orthorhombic structure is released. The package called ortho-elastic. The formalism of calculating the ortho-elastic constants is described in details. The package is compatible with the highly accurate all-electron full-potential (linearized) augmented plane-wave plus local orbital [FP-(L)APW+lo] method implemented in WIEN2k code. Several orthorhombic structure compounds were used to test the new package. We found that the calculated elastic constants using the new package show better agreement with the available experimental data than the previous theoretical results used different methods. In this package the second-order derivative E ″ (ε) of polynomial fit E=E(ε) of energy vs strains at zero strain (ε=0), used to calculate the orthorhombic elastic constants.

  20. 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.

  1. 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.

  2. 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.

  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

    2015-03-05

    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.

  4. Vibrational, structural and electronic properties investigation by DFT calculations and molecular docking studies with DNA topoisomerase II of strychnobrasiline type alkaloids: A theoretical approach for potentially bioactive molecules

    Science.gov (United States)

    Costa, Renyer A.; Oliveira, Kelson M. T.; Costa, Emmanoel Vilaça; Pinheiro, Maria L. B.

    2017-10-01

    A combined experimental and theoretical DFT study of the structural, vibrational and electronic properties of strychnobrasiline and 12-hydroxy-10,11-dimethoxystrychnobrasiline is presented using the Becke three-parameter Lee-Yang-Parr function (B3LYP) and 6-311G(2d,p) basis set. The theoretical geometry optimization data were compared with the X-ray data for a similar structure in the associated literature, showing close values. The calculated HOMO-LUMO gap values showed that the presence of substituents in the benzene ring influences the quantum properties which are directly related to the reactive properties. Theoretical UV spectra agreed well with the measured experimental data, with bands assigned. In addition, Natural Bond Orbitals (NBOs), Mapped molecular electrostatic potential surface (MEPS) and NLO calculations were also performed at the same theory level. The theoretical vibrational analysis revealed several characteristic vibrations that may be used as a diagnostic tool for other strychnobrasiline type alkaloids, simplifying their identification and structural characterization. Molecular docking calculations with DNA Topoisomerase II-DNA complex showed binding free energies values of -8.0 and -9.5 kcal/mol for strychnobrasiline and 12-hydroxy-10,11-dimethoxystrychnobrasiline respectively, while for amsacrine, used for the treatment of leukemia, the binding free energy ΔG presented a value of -10.0 kcal/mol, suggesting that strychnobrasiline derivative alkaloids might exhibit an antineoplastic activity.

  5. The synergetic effect of V and Fe-co-doping in TiO{sub 2} studied from the DFT + U first-principle calculation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Baoshun, E-mail: liubaoshun@126.com; Zhao, Xiujian

    2017-03-31

    Highlights: • The effect of Fe and V doping on TiO{sub 2} structure was studied with DFT + U calculation. • V and Fe co-doping affects the formation energies and electronic structure. • V and Fe co-doping causes the synergetic effect on the optical properties. - Abstract: Based on the density functional theory (DFT + U), a detailed study on the energetic, electronic, and optical properties of Fe-, V-, and Fe & V-co-doping anatase and rutile TiO{sub 2} was performed The synergetic effect of Fe & V bimetal co-doping on the optical absorption was discussed on electronic level. Two kinds of co-dopants were considered, which included edge-shared and corner-shared co-doping. It was shown that Fe and V atoms prefer to replace Ti atom in the O-rich contions than in the Ti-rich conditions. Co-doping in anatase reduces the formation energies in both cases, while the formation energies for rutile cannot be decreased. The Bader charge analysis indicates the +3 of Fe atom and +4 of V atom, and the obvious electron exchange between Fe and V atom in co-doping cases can be identified, which indicates the presence of synergetic effect induced by co-doping. The cooperation of Fe & V co-dopants was also supported by the result of projected density of states and spin charge density differences, as the hybridization of Fe3d with V3d orbitals was seen within the TiO{sub 2} forbidden band. Different from single-dopant systems, the V3d-Fe3d co-interaction leads to the formation of some spin mid-gap states, which have an obvious effect on the optical absorptions.

  6. Structural characterization, vibrational spectroscopy accomplished with DFT calculation, thermal and dielectric behaviors in a new organic-inorganic tertrapropylammonium aquapentachlorostannate dihydrate compound

    Energy Technology Data Exchange (ETDEWEB)

    Hajlaoui, Sondes, E-mail: hajlaouisondes@yahoo.fr [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia); Chaabane, Iskandar [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia); Lhoste, Jérôme; Bulou, Alain [LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085, Le Mans, Cedex 9 (France); Guidara, Kamel [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia)

    2016-09-15

    In this work a novel compound tertrapropylammonium aquapentachlorostannate dihydrate was synthesized and characterized by; single crystal X-ray diffraction, vibrational spectroscopy, differential scanning calorimetric and dielectric measurement. The crystal structure refinement at room temperature reveled that this later belongs to the monoclinic compound with P121/c1 space group with the following unit cell parameters a = 8.2699(3) Å, b = 12.4665(4) Å, c = 22.3341(7) Å and β = 92.94(0)°. The crystal arrangement can be described by stacked organic-inorganic layers in the c direction with two independent water molecules placed between each two layers. The detailed interpretations of the vibrational properties of the studied compound were performed using density functional theory (DFT) with the B3LYP/LanL2DZ basis set, and has enabled us to make the detailed assignments by comparative study of the experimental and calculated Raman and IR spectra. The differential scanning calorimetry (DSC) measurement disclosed two anomalies in the temperature range 356–376 (T{sub 1}) K and at 393 K (T{sub 2}) characterized by the dehydration of the sample and probably a reconstruction of a new structure after T{sub 2} transition. The temperature dependences of dielectric permittivity show a relaxation process around T{sub 2} anomaly indicating the occurrence of the disorder at high temperature. The dependence of the exponent m(T) on temperature, extracted from the straight lines of log(ε″) with log (ω), suggests that the correlated barrier hopping is the appropriate model for the conduction mechanism. - Highlights: • The single-crystal X-ray diffraction has been performed. • The assignments of the vibration modes based on DFT were reported and discussed. • Differential scanning calorimetric reveals the presence of two endothermic peaks. • The electric permittivity was studied using the impedance measurements. • The CBH is the appropriate model for the conduction

  7. Electronic structure, magnetism, and exchange integrals in transition-metal oxides: Role of the spin polarization of the functional in DFT+U calculations

    Science.gov (United States)

    Keshavarz, Samara; Schött, Johan; Millis, Andrew J.; Kvashnin, Yaroslav O.

    2018-05-01

    Density functional theory augmented with Hubbard-U corrections (DFT+U ) is currently one of the most widely used methods for first-principles electronic structure modeling of insulating transition-metal oxides (TMOs). Since U is relatively large compared to bandwidths, the magnetic excitations in TMOs are expected to be well described by a Heisenberg model. However, in practice the calculated exchange parameters Ji j depend on the magnetic configuration from which they are extracted and on the functional used to compute them. In this work we investigate how the spin polarization dependence of the underlying exchange-correlation functional influences the calculated magnetic exchange constants of TMOs. We perform a systematic study of the predictions of calculations based on the local density approximation plus U (LDA+U ) and the local spin density approximation plus U (LSDA+U ) for the electronic structures, total energies, and magnetic exchange interactions Ji j extracted from ferromagnetic (FM) and antiferromagnetic (AFM) configurations of several transition-metal oxide materials. We report that for realistic choices of Hubbard U and Hund's J parameters, LSDA+U and LDA+U calculations result in different values of the magnetic exchange constants and band gap. The dependence of the band gap on the magnetic configuration is stronger in LDA+U than in LSDA+U and we argue that this is the main reason why the configuration dependence of Ji j is found to be systematically more pronounced in LDA+U than in LSDA+U calculations. We report a very good correspondence between the computed total energies and the parametrized Heisenberg model for LDA+U calculations, but not for LSDA+U , suggesting that LDA+U is a more appropriate method for estimating exchange interactions.

  8. Study of half-metallic behavior in Sr2CoWO6 perovskite by ab initio DFT calculations

    International Nuclear Information System (INIS)

    Bonilla, M.; Landinez Tellez, D.A.; Arbey Rodriguez, J.; Aguiar, J. Albino; Roa-Rojas, J.

    2008-01-01

    In this work, we report several ab initio calculations performed for Sr 2 CoWO 6 by means of the density functional theory and the linearized augmented plane wave method for both spin orientations. For calculations, the exchange and correlation potential were treated into the generalized gradient approximation, which permits to consider from the beginning the difference between the electronic densities for both up and down spin orientations. The densities of states are calculated by the histogram method and the positions of Fermi levels are found by integrating over the density of states for both spin configurations. Our results reveal that Sr 2 CoWO 6 material behaves as insulators for the spin-up orientation and conductor for the spin down, as expected for the half-metallic systems. Results of partial densities of states permit to conclude that the conduction band has predominant contributions of d x 2 -y 2 and d xz+yz states of Co for the spin-down orientation. A magnetic moment of 3 μ B was calculated. From the Murnaghan equation state, we also calculate the cell dimensions that minimize the total energy for several configurations

  9. Electronic structure of BaFe2As2 as obtained from DFT/ASW first-principles calculations

    KAUST Repository

    Schwingenschlö gl, Udo; Di Paola, Cono

    2010-01-01

    We use ab-initio calculations based on the augmented spherical wave method within density functional theory to study the magnetic ordering and Fermi surface of BaFe2As2, the parent compound of the hole-doped iron pnictide superconductors (K,Ba)Fe2As

  10. 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.

  11. Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

    Science.gov (United States)

    Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

    2018-04-01

    Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

  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 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.

  14. Interaction of fisetin with human serum albumin by fluorescence, circular dichroism spectroscopy and DFT calculations: binding parameters and conformational changes

    International Nuclear Information System (INIS)

    Matei, Iulia; Ionescu, Sorana; Hillebrand, Mihaela

    2011-01-01

    The interaction between fisetin, an antioxidant and neuroprotective flavonoid, and human serum albumin (HSA) is investigated by means of fluorescence (steady-state, synchronous, time-resolved) and circular dichroism (CD) spectroscopy. The formation of a 1:1 complex with a constant of about 10 5 M -1 was evidenced. Foerster's resonance energy transfer and competitive binding with site markers warfarin and ibuprofen were considered and discussed. Changes in the CD band of HSA indicate a decrease in the α-helix content upon binding. An induced CD signal for bound fisetin was observed and rationalized in terms of density functional theory calculations. - Highlights: → Fisetin-BSA system was studied by fluorescence spectroscopy. → Binding parameters, association constant and number of sites were estimated. → Binding site of fisetin was identified by competitive experiments. → Conformational changes in HSA and fisetin were evidenced by circular dichroism. → TDDFT calculated CD spectra supported the experimental data.

  15. Interaction of fisetin with human serum albumin by fluorescence, circular dichroism spectroscopy and DFT calculations: binding parameters and conformational changes

    Energy Technology Data Exchange (ETDEWEB)

    Matei, Iulia; Ionescu, Sorana [Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta 4-12, 030018 Bucharest (Romania); Hillebrand, Mihaela, E-mail: mihh@gw-chimie.math.unibuc.ro [Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta 4-12, 030018 Bucharest (Romania)

    2011-08-15

    The interaction between fisetin, an antioxidant and neuroprotective flavonoid, and human serum albumin (HSA) is investigated by means of fluorescence (steady-state, synchronous, time-resolved) and circular dichroism (CD) spectroscopy. The formation of a 1:1 complex with a constant of about 10{sup 5} M{sup -1} was evidenced. Foerster's resonance energy transfer and competitive binding with site markers warfarin and ibuprofen were considered and discussed. Changes in the CD band of HSA indicate a decrease in the {alpha}-helix content upon binding. An induced CD signal for bound fisetin was observed and rationalized in terms of density functional theory calculations. - Highlights: > Fisetin-BSA system was studied by fluorescence spectroscopy. > Binding parameters, association constant and number of sites were estimated. > Binding site of fisetin was identified by competitive experiments. > Conformational changes in HSA and fisetin were evidenced by circular dichroism. > TDDFT calculated CD spectra supported the experimental data.

  16. Electronic structure of BaFe2As2 as obtained from DFT/ASW first-principles calculations

    KAUST Repository

    Schwingenschlögl, Udo

    2010-07-02

    We use ab-initio calculations based on the augmented spherical wave method within density functional theory to study the magnetic ordering and Fermi surface of BaFe2As2, the parent compound of the hole-doped iron pnictide superconductors (K,Ba)Fe2As2, for the tetragonal I4/mmm as well as the orthorhombic Fmmm structure. In comparison to full potential linear augmented plane wave calculations, we obtain significantly smaller magnetic energies. This finding is remarkable, since the augmented spherical wave method, in general, is known for a most reliable description of magnetism. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

    Science.gov (United States)

    2017-10-31

    VC-nH2O for Small and Water-Dominated Molecular Clusters October 31, 2017 Approved for public release; distribution is unlimited. L. Huang S.g...Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters L. Huang,1 S.G...nH2O molecular clusters using density function theory (DFT). DFT can provide interpretation of absorption spectra with respect to molecular

  18. Adsorption of F2C=CFCl on TiO2 nano-powder: Structures, energetics and vibrational properties from DRIFT spectroscopy and periodic quantum chemical calculations

    International Nuclear Information System (INIS)

    Tasinato, Nicola; Moro, Daniele; Stoppa, Paolo; Pietropolli Charmet, Andrea; Toninello, Piero; Giorgianni, Santi

    2015-01-01

    Graphical abstract: - Highlights: • Adsorption of F 2 C=CFCl on TiO 2 unveiled by DRIFTS and periodic DFT. • Structural, energetic and vibrational properties of F 2 C=CFCl @ anatase (1 0 1). • Binding energies (B3LYP-D2) between −17 and −46 kJ mol −1 depending on the anchor point. • Theory and experiment converge on the CF 2 moiety as the main anchor point. - Abstract: Photodegradation over titanium dioxide (TiO 2 ) is a very appealing technology for removing environmental pollutants from the air, the adsorption interaction being the first step of the whole reaction pathway. In the present work the adsorption of F 2 C=CFCl (chlorotrifluoroethene, halon 1113), a compound used by industry and detected in the atmosphere, on a commercial TiO 2 nano-powder is investigated experimentally by in situ DRIFT spectroscopy and theoretically through periodic ab initio calculations rooted in DFT. The spectra of the adsorbed molecule suggest that the anchoring to the surface mainly takes place through F atoms. Theoretically, five adsorption configurations for the molecule interacting with the anatase (1 0 1) surface are simulated at B3LYP level and for each of them, structures, binding energies and vibrational frequencies are derived. The interplay between theory and experiments shows the coexistence of different adsorption configurations, the foremost ones featuring the interaction of one F atom with a fivefold coordinated Ti 4+ of the surface. These two adsorption models, which mostly differ for the orientation of the adsorbate with respect to the surface, feature a binding energy of −45.6 and −41.0 kJ mol −1 according to dispersion corrected DFT calculations. The favorable adsorption interaction appears as an important requirement toward the application of titanium dioxide technologies for the photocatalytic degradation of halon 1113.

  19. The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment.

    Science.gov (United States)

    Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M

    2018-01-05

    Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag 2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514nm and the SERS spectra at 785 and 514nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag 2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag 2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 10 4 , was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering

  20. 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.

  1. The nature of the Pt(111)/α -Fe2O3(0001) interfaces revealed by DFT calculations

    Science.gov (United States)

    Mahmoud, Agnes; Deleuze, Pierre-Marie; Dupont, Céline

    2018-05-01

    Density functional theory calculations are performed to give a thorough description of structural, energetic, and electronic properties of Pt(111)/α-Fe2O3(0001) systems by spin-polarized calculations, accounting for the on-site Coulomb interaction. Toward the better understanding of Pt(111)/α-Fe2O3(0001) interfaces, two terminations of α-Fe2O3(0001) surface, namely, the single Fe- and the O3-termination, are considered and coupled with the four possible (top, hcp, fcc, and bridge) sites on Pt(111). The effect of the strain on clean hematite surfaces due to the lattice mismatch between the substrate and the overlayer is included in the analysis. Among the possible adsorption configurations, bridge sites are unstable, while the most favorable configurations are the ones at hollow sites. The stability of the interfaces is not only influenced by the termination of the overlayer but also influenced by the degree of its structural relaxation and the relative position of the first layer of O atoms in hematite with respect to Pt. To elucidate the different nature of the two terminations of the overlayer on Pt, projected density of states and 3D charge density difference plots are also discussed.

  2. Analysis of the electronic structures of 3d transition metals doped CuGaS2 based on DFT calculations

    International Nuclear Information System (INIS)

    Zhao Zongyan; Zhou Dacheng; Yi Juan

    2014-01-01

    3d transition metals doped CuGaS 2 are considered as possible absorbing material candidates for intermediated band thin film solar cells. The electronic structure and optical properties of 3d transition metals doped CuGaS 2 are investigated by using density functional theory calculations with the GGA + U method in the present work. The doping with 3d transition metals does not obviously change the crystal structure, band gap, and optical absorption edge of the CuGaS 2 host. However, in the case of CuGa 1−x TM x S 2 (TM = Ti, V, Cr, Fe, and Ni), there is at least one distinct isolated impurity energy level in the band gap, and the optical absorption is enhanced in the ultraviolet-light region. Therefore, these materials are ideal absorber material candidates for intermediated band thin film solar cells. The calculated results are very well consistent with experimental observations, and could better explain them. (semiconductor materials)

  3. Synthesis, characterization and DFT calculations of electronic and optical properties of CaMoO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Bouzidi, Chaker, E-mail: bouzidtc@yahoo.fr [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Horchani-Naifer, Karima; Khadraoui, Zied [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Elhouichet, Habib [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia); Département de Physique, Faculté des Sciences de Tunis, Université de Tunis-ElManar ElManar, 2092 Tunis (Tunisia); Ferid, Mokhtar [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National des Recherches en Sciences des Matériaux, BP No.73, 8027 Soliman (Tunisia)

    2016-09-15

    The electronic and optical properties of calcium molybdate (CaMoO{sub 4}) have been determined by X-ray diffraction, spectroscopic measurements and calculations of energy-band structures, density of states, and optical response functions by density functional theory. The chemical bonding analysis indicates that Mo–O bonds exhibit more covalent character than the Ca–O bond. The linear photon-energy-dependent dielectric functions, conductivity, refractive index, reflectivity and extinction coefficients were investigated and analyzed. The results are in agreement with previous theoretical works and the experimental data. Reflectivity spectra revealed that the CaMoO{sub 4} promises as good coating materials in the energy region of 9.3–11.6 eV with reflectivity larger than 75%.

  4. High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO3 perovskites

    Science.gov (United States)

    Emery, Antoine A.; Wolverton, Chris

    2017-10-01

    ABO3 perovskites are oxide materials that are used for a variety of applications such as solid oxide fuel cells, piezo-, ferro-electricity and water splitting. Due to their remarkable stability with respect to cation substitution, new compounds for such applications potentially await discovery. In this work, we present an exhaustive dataset of formation energies of 5,329 cubic and distorted perovskites that were calculated using first-principles density functional theory. In addition to formation energies, several additional properties such as oxidation states, band gap, oxygen vacancy formation energy, and thermodynamic stability with respect to all phases in the Open Quantum Materials Database are also made publicly available. This large dataset for this ubiquitous crystal structure type contains 395 perovskites that are predicted to be thermodynamically stable, of which many have not yet been experimentally reported, and therefore represent theoretical predictions. The dataset thus opens avenues for future use, including materials discovery in many research-active areas.

  5. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-11-14

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  6. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2013-01-01

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  7. On the interplay between chirality and exciton coupling: a DFT calculation of the circular dichroism in π-stacked ethylene.

    Science.gov (United States)

    Norman, Patrick; Linares, Mathieu

    2014-09-01

    The chirality of stacked weakly interacting π-systems was interpreted in terms of Frenkel exciton states and the formation of excitonic circular dichroism (CD) bands was monitored for ethylene stacks of varying sizes. Convergence of CD bands with respect to the system size was observed for stacks involving around 10 molecules. By means of rotation around the C-C double bond in ethylene, chirality was induced in the monomeric system and which was shown to dominate the spectral responses, even for polymer aggregates. In helical assemblies of chiral entities, there will always be a mix of excitonic and monomeric contributions to the CD signal and it is demonstrated that the complex polarization propagator approach in combination with Density Functional Theory is a suitable method to address this situation. © 2014 Wiley Periodicals, Inc.

  8. 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.

  9. 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.

  10. Efficient, approximate and parallel Hartree-Fock and hybrid DFT calculations. A 'chain-of-spheres' algorithm for the Hartree-Fock exchange

    International Nuclear Information System (INIS)

    Neese, Frank; Wennmohs, Frank; Hansen, Andreas; Becker, Ute

    2009-01-01

    In this paper, the possibility is explored to speed up Hartree-Fock and hybrid density functional calculations by forming the Coulomb and exchange parts of the Fock matrix by different approximations. For the Coulomb part the previously introduced Split-RI-J variant (F. Neese, J. Comput. Chem. 24 (2003) 1740) of the well-known 'density fitting' approximation is used. The exchange part is formed by semi-numerical integration techniques that are closely related to Friesner's pioneering pseudo-spectral approach. Our potentially linear scaling realization of this algorithm is called the 'chain-of-spheres exchange' (COSX). A combination of semi-numerical integration and density fitting is also proposed. Both Split-RI-J and COSX scale very well with the highest angular momentum in the basis sets. It is shown that for extended basis sets speed-ups of up to two orders of magnitude compared to traditional implementations can be obtained in this way. Total energies are reproduced with an average error of <0.3 kcal/mol as determined from extended test calculations with various basis sets on a set of 26 molecules with 20-200 atoms and up to 2000 basis functions. Reaction energies agree to within 0.2 kcal/mol (Hartree-Fock) or 0.05 kcal/mol (hybrid DFT) with the canonical values. The COSX algorithm parallelizes with a speedup of 8.6 observed for 10 processes. Minimum energy geometries differ by less than 0.3 pm in the bond distances and 0.5 deg. in the bond angels from their canonical values. These developments enable highly efficient and accurate self-consistent field calculations including nonlocal Hartree-Fock exchange for large molecules. In combination with the RI-MP2 method and large basis sets, second-order many body perturbation energies can be obtained for medium sized molecules with unprecedented efficiency. The algorithms are implemented into the ORCA electronic structure system

  11. Synthesis, crystal structure, spectroscopic characterization, Hirshfeld surface analysis, and DFT calculations of 1,4-dimethyl-2-oxo-pyrimido[1,2-a]benzimidazole hydrate

    Science.gov (United States)

    El Bakri, Youness; Anouar, El Hassane; Ramli, Youssef; Essassi, El Mokhtar; Mague, Joel T.

    2018-01-01

    Imidazopyrimidine derivatives are organic synthesized compounds with a pyrimido[1,2-a]benzimidazole as basic skeleton. They are known for their various biological properties and as an important class of compounds in medicinal chemistry. A new 1,4-dimethyl-2-oxo-pyrimido[1,2-a]benzimidazole hydrate derivative of the tilted group has been synthesized and characterized by spectroscopic techniques NMR and FT-IR; and by a single crystal X-ray diffraction. The X-ray results showed that the tricyclic core of the title compound, C12H11N3O·H2O, is almost planar. The molecules stack along the a-axis direction in head-to- tail fashion through π-stacking interactions involving all three rings. The stacks are tied together by direct Csbnd H⋯O hydrogen bonds and by Osbnd H⋯O, Osbnd N⋯N and Csbnd H⋯O hydrogen bonds with the lattice water. DFT calculations at B3LYP/6-311++G(d,p) in gas phase an polarizable continuum model have been carried out to predict the spectral and geometrical data of the tilted compound. The obtained results showed relatively good correlations between the predicted and experimental data with correlation coefficients higher than 98%.

  12. 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.

  13. Structural determination of stable MoO{sub x} monolayers on O/Cu{sub 3}Au(1 0 0): DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Valadares, George C.S., E-mail: georgevaladares@if.ufrj.br [Instituto de Fisica, Universidade Federal do Rio de Janeiro, Caixa Postal 68528, Rio de Janeiro, RJ 21941-972 (Brazil); Mendes, F.M.T. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Instituto Nacional de Tecnologia, Av. Venezuela 82, Centro, Rio de Janeiro, RJ 20081-312 (Brazil); Dionizio Moreira, M. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Universidade Federal do Triangulo Mineiro, Instituto de Ciencias Exatas, Naturais e Educacao, Av. Getulio Guarita, 159, Bairro Abadia, CEP.: 38025-180, Uberaba, MG (Brazil); Leitao, A.A. [Departamento de Quimica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG 36036-330 (Brazil); Niehus, H. [Divisao de Metrologia de Materiais (DIMAT), Instituto Nacional de Metrologia, Normalizacao e Qualidade Industrial (Inmetro), CEP 25250-020, Xerem, Duque de Caxias, RJ (Brazil); Institut fuer Physik, Humboldt Universitaet zu Berlin, Newtonstrasse 15, Berlin 12489 (Germany); and others

    2012-10-08

    Highlights: Black-Right-Pointing-Pointer Molybdenum oxide is widely used in catalysis in the chemical industry. Black-Right-Pointing-Pointer Recently, ultra-thin (monolayer) films of MoO{sub x} have been produced on top of O-Cu{sub 3}Au substrates. Black-Right-Pointing-Pointer XPS measurements suggest an unusual +5 charge state of the Mo cation. Black-Right-Pointing-Pointer Seeking for a low-energy structure with good match to the experimental STM and XPS. Black-Right-Pointing-Pointer Bader charges indicate indeed an intermediate charge state as compared to the more common Mo{sup +4}O{sub 2} and Mo{sup +6}O{sub 3} bulk oxides. -- Abstract: Using ab initio calculations based on density functional theory (DFT), we propose a geometrical structure for MoO{sub x} monolayers recently grown on O/Cu{sub 3}Au(1 0 0) substrates. The proposed structure reproduces the p(2 Multiplication-Sign 2) symmetry found by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED), as well as the intermediate oxidation state between Mo(IV) and Mo(VI) identified by X-ray photoelectron spectroscopy (XPS). Simulated STM images assign the bright spots in the experimental images to oxygen 2p states.

  14. Synthesis, growth, physicochemical properties and DFT calculations of 2-naphthol substituted Mannich base 1-(morpholino(phenyl) methyl) naphthalen-2-ol: A non linear optical single crystal

    Science.gov (United States)

    Dennis Raj, A.; Jeeva, M.; Shankar, M.; Venkatesa Prabhu, G.; Vimalan, M.; Vetha Potheher, I.

    2017-11-01

    2-Naphthol substituted Mannich base 1-morpholino(phenyl)methyl)naphthalen-2-ol (MPMN), a potential NLO active organic single crystal was developed using acetonitrile as a solvent by slow evaporation method. The experimental and theoretical analysis made towards the exploitation in the field of electro-optic and NLO applications. The cubic structure with non-centrosymmetric space group Cc was confirmed and cell dimensions of the grown crystal were obtained from single crystal X-ray diffraction (XRD) study. The formation of the Csbnd Nsbnd C vibrational band at 1115 cm-1 in Fourier Transform Infra-Red (FTIR) analysis confirms the formation of MPMN compound. The placement of protons and carbons of MPMN were identified from Nuclear Magnetic Resonance Spectroscopy (NMR) analysis. The wide optical absorption window and the lower cutoff wavelength of MPMN show the suitability of the material for the various laser related applications. The presence of dislocations and growth pattern of crystal were analyzed using chemical etching technique. The Second Harmonic Generation (SHG) of MPMN was found to be 1.57 times greater than the standard KDP crystal. The laser damage threshold was measured by using Nd: YAG laser beam passed through the sample and it was found to be 1.006 GW/cm2. The electronic structure of the molecular system and the optical properties were also studied from quantum chemical calculations using Density Functional Theory (DFT) and reported for the first time.

  15. Study of morphology effects on magnetic interactions and band gap variations for 3d late transition metal bi-doped ZnO nanostructures by hybrid DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Datta, Soumendu, E-mail: soumendu@bose.res.in; Baral, Sayan; Mookerjee, Abhijit [Department of Condensed Matter Physics and Material Sciences, S.N. Bose National Centre for Basic Sciences, JD Block, Sector-III, Salt Lake City, Kolkata 700 098 (India); Kaphle, Gopi Chandra [Central Department of Physics, Tribhuvan University, Kathmandu (Nepal)

    2015-08-28

    Using density functional theory (DFT) based electronic structure calculations, the effects of morphology of semiconducting nanostructures on the magnetic interaction between two magnetic dopant atoms as well as a possibility of tuning band gaps have been studied in the case of the bi-doped (ZnO){sub 24} nanostructures with the impurity dopant atoms of the 3d late transition metals—Mn, Fe, Co, Ni, and Cu. To explore the morphology effect, three different structures of the host (ZnO){sub 24} nano-system, having different degrees of spatial confinement, have been considered: a two dimensional nanosheet, a one dimensional nanotube, and a finite cage-shaped nanocluster. The present study employs hybrid density functional theory to accurately describe the electronic structure of all the systems. It is shown here that the magnetic coupling between the two dopant atoms remains mostly anti-ferromagnetic in the course of changing the morphology from the sheet geometry to the cage-shaped geometry of the host systems, except for the case of energetically most stable bi-Mn doping, which shows a transition from ferromagnetic to anti-ferromagnetic coupling with decreasing aspect ratio of the host system. The effect of the shape change, however, has a significant effect on the overall band gap variations of both the pristine as well as all the bi-doped systems, irrespective of the nature of the dopant atoms and provides a means for easy tunability of their optoelectronic properties.

  16. A new method suitable for calculating accurately wetting temperature over a wide range of conditions: Based on the adaptation of continuation algorithm to classical DFT

    Science.gov (United States)

    Zhou, Shiqi

    2017-11-01

    A new scheme is put forward to determine the wetting temperature (Tw) by utilizing the adaptation of arc-length continuation algorithm to classical density functional theory (DFT) used originally by Frink and Salinger, and its advantages are summarized into four points: (i) the new scheme is applicable whether the wetting occurs near a planar or a non-planar surface, whereas a zero contact angle method is considered only applicable to a perfectly flat solid surface, as demonstrated previously and in this work, and essentially not fit for non-planar surface. (ii) The new scheme is devoid of an uncertainty, which plagues a pre-wetting extrapolation method and originates from an unattainability of the infinitely thick film in the theoretical calculation. (iii) The new scheme can be similarly and easily applied to extreme instances characterized by lower temperatures and/or higher surface attraction force field, which, however, can not be dealt with by the pre-wetting extrapolation method because of the pre-wetting transition being mixed with many layering transitions and the difficulty in differentiating varieties of the surface phase transitions. (iv) The new scheme still works in instance wherein the wetting transition occurs close to the bulk critical temperature; however, this case completely can not be managed by the pre-wetting extrapolation method because near the bulk critical temperature the pre-wetting region is extremely narrow, and no enough pre-wetting data are available for use of the extrapolation procedure.

  17. 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.

  18. Investigation on the electronic structures and photophysical properties of a series of cyclometalated iridium(III) complexes based on DFT/TDDFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Chunyu, E-mail: shang.chun.yu@163.com; Xu, Jie; Du, Yanqiu; Zhao, Jie

    2016-07-15

    The electronic structures and photophysical properties of a series of cyclometalated iridium (III) complexes Ir(C{sup ∧}N){sub 2}(H{sub 2}NNHCOO), including 1 [C{sup ∧}N=2-phenyl-pyridine], 2 [C{sup ∧}N=5-fluoro-2-phenylpyridine], 3 [C{sup ∧}N=2-phenyl-5-trifluoromethylpyridine], 4 [C{sup ∧}N=6-phenyl-[2, 3] bipyridinyl], 5 [C{sup ∧}N=7-phenyl-cyclopenta [4] dipyridine] and 6 [C{sup ∧}N=8-phenyl-[1, 9] phenanthroline], have been theoretically investigated based on density functional theory (DFT) and time-dependent DFT. The characteristics in phosphorescent performances have been outlined for each of the complexes in the applications in OLED. On the basis of the two simplifications presented in this paper and the available experimental data, the magnitudes of phosphorescent radiative rates for complexes 1–6 were approximately calculated to be: 5.56×10{sup 5} s{sup −1}, 2.68×10{sup 5} s{sup −1}, 1.17×10{sup 6} s{sup −1}, 9.78×10{sup 4} s{sup −1}, 5.30×10{sup 6} s{sup −1} and 6.71×10{sup 6} s{sup −1}, respectively. Meanwhile, the sequence of phosphorescent quantum efficiencies was obtained to be: Φ{sub PL}(4)<Φ{sub PL}(2)<Φ{sub PL}(1)<Φ{sub PL}(3)<Φ{sub PL}(5)<Φ{sub PL}(6), in which Φ{sub PL}(4) is by far the lowest, Φ{sub PL}(5) is much larger and Φ{sub PL}(6) is by far the largest. In contrast to complex 1, the emission wavelengths are slightly red-shifted for 2 and 3 and significantly red-shifted for 4 and 5, while the emission wavelength of 6 is slightly blue-shifted. In comparison, complexes 6 and 5 may be singled out to be the most efficient phosphorescence emitters for the applications in OLED.

  19. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu

    2014-01-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study

  20. New insights into the origin of visible-light photocatalytic activity in Se-modified anatase TiO2 from screened coulomb hybrid DFT calculations

    KAUST Repository

    Harb, Moussab

    2013-12-05

    We report a systematic study on the optoelectronic properties of Se-modified anatase TiO2 investigated by DFT (including the perturbation theory approach DFPT) within the screened coulomb hybrid HSE06 formalism to guarantee accurate band gap and electronic excitation predictions. Various selenium species at substitutional sites for O or Ti, at interstitial sites, as well as at mixed substitutional/interstitial sites are studied. Among the explored structures, Ti(1-2x)O2Se2x (containing Se4+ species), TiO(2-x)Sex (containing Se2- species), and TiO(2-x)Se2x (containing Se2 2- species) reveal significant enhanced visible-light optical absorption spectra with new absorption features appearing at 500, 600, and 690 nm, respectively. Our calculated spectra are found to be in good agreement with those obtained in available experimental works. The band gap narrowing in these materials originates from incorporation of newly occupied electronic levels within 0.5-1.5 eV above the original valence band of TiO 2, leading to new narrowed band gaps of 2.5, 2.0, and 1.8 eV respectively. Our calculations also reveal suitable band positions of Ti (1-2x)O2Se2x and TiO(2-x)Se x for overall water splitting, whereas TiO(2-x)Se 2x shows an unsuitable valence band position for the oxygen evolution reaction. In contrast, the localized electronic character of the new occupied states on the Se 4p orbitals and only on the O 2p orbitals linked to the Se species makes the holes mobility limited in this material and the recombination rate of charge carriers greatly increased in the bulk. © 2013 American Chemical Society.

  1. Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations

    Science.gov (United States)

    Slavova-Kazakova, Adriana K; Angelova, Silvia E; Veprintsev, Timur L; Denev, Petko; Fabbri, Davide; Dettori, Maria Antonietta; Kratchanova, Maria; Naumov, Vladimir V; Trofimov, Aleksei V; Vasil’ev, Rostislav F

    2015-01-01

    Summary This study compares the ability to scavenge different peroxyl radicals and to act as chain-breaking antioxidants of monomers related to curcumin (1): dehydrozingerone (2), zingerone (3), (2Z,5E)-ethyl 2-hydroxy-6-(4-hydroxy-3-methoxyphenyl)-4-oxohexa-2,5-dienoate (4), ferulic acid (5) and their corresponding C 2-symmetric dimers 6–9. Four models were applied: model 1 – chemiluminescence (CL) of a hydrocarbon substrate used for determination of the rate constants (k A) of the reactions of the antioxidants with peroxyl radicals; model 2 – lipid autoxidation (lipidAO) used for assessing the chain-breaking antioxidant efficiency and reactivity; model 3 – oxygen radical absorbance capacity (ORAC), which yields the activity against peroxyl radicals generated by an azoinitiator; model 4 – density functional theory (DFT) calculations at UB3LYP/6-31+G(d,p) level, applied to explain the structure–activity relationship. Dimers showed 2–2.5-fold higher values of k A than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant activity for monomers and dimers with α,β-unsaturated side chains. Curcumin and 6 in fact are dimers of the same monomer 2. We conclude that the type of linkage between the two “halves” by which the molecule is made up does not exert influence on the antioxidant efficiency and reactivity of these two dimers. The dimers and the monomers demonstrated higher activity than Trolox (10) in aqueous medium (model 3). A comparison of the studied compounds with DL-α-tocopherol (11), Trolox and curcumin is made. All dimers are characterized through lower bond dissociation enthalpies (BDEs) than their monomers (model 4), which qualitatively supports the experimental results. PMID:26425195

  2. Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC and DFT calculations

    Directory of Open Access Journals (Sweden)

    Adriana K. Slavova-Kazakova

    2015-08-01

    Full Text Available This study compares the ability to scavenge different peroxyl radicals and to act as chain-breaking antioxidants of monomers related to curcumin (1: dehydrozingerone (2, zingerone (3, (2Z,5E-ethyl 2-hydroxy-6-(4-hydroxy-3-methoxyphenyl-4-oxohexa-2,5-dienoate (4, ferulic acid (5 and their corresponding C2-symmetric dimers 6–9. Four models were applied: model 1 – chemiluminescence (CL of a hydrocarbon substrate used for determination of the rate constants (kA of the reactions of the antioxidants with peroxyl radicals; model 2 – lipid autoxidation (lipidAO used for assessing the chain-breaking antioxidant efficiency and reactivity; model 3 – oxygen radical absorbance capacity (ORAC, which yields the activity against peroxyl radicals generated by an azoinitiator; model 4 – density functional theory (DFT calculations at UB3LYP/6-31+G(d,p level, applied to explain the structure–activity relationship. Dimers showed 2–2.5-fold higher values of kA than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant activity for monomers and dimers with α,β-unsaturated side chains. Curcumin and 6 in fact are dimers of the same monomer 2. We conclude that the type of linkage between the two “halves” by which the molecule is made up does not exert influence on the antioxidant efficiency and reactivity of these two dimers. The dimers and the monomers demonstrated higher activity than Trolox (10 in aqueous medium (model 3. A comparison of the studied compounds with DL-α-tocopherol (11, Trolox and curcumin is made. All dimers are characterized through lower bond dissociation enthalpies (BDEs than their monomers (model 4, which qualitatively supports the experimental results.

  3. Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations.

    Science.gov (United States)

    Slavova-Kazakova, Adriana K; Angelova, Silvia E; Veprintsev, Timur L; Denev, Petko; Fabbri, Davide; Dettori, Maria Antonietta; Kratchanova, Maria; Naumov, Vladimir V; Trofimov, Aleksei V; Vasil'ev, Rostislav F; Delogu, Giovanna; Kancheva, Vessela D

    2015-01-01

    This study compares the ability to scavenge different peroxyl radicals and to act as chain-breaking antioxidants of monomers related to curcumin (1): dehydrozingerone (2), zingerone (3), (2Z,5E)-ethyl 2-hydroxy-6-(4-hydroxy-3-methoxyphenyl)-4-oxohexa-2,5-dienoate (4), ferulic acid (5) and their corresponding C 2-symmetric dimers 6-9. Four models were applied: model 1 - chemiluminescence (CL) of a hydrocarbon substrate used for determination of the rate constants (k A) of the reactions of the antioxidants with peroxyl radicals; model 2 - lipid autoxidation (lipidAO) used for assessing the chain-breaking antioxidant efficiency and reactivity; model 3 - oxygen radical absorbance capacity (ORAC), which yields the activity against peroxyl radicals generated by an azoinitiator; model 4 - density functional theory (DFT) calculations at UB3LYP/6-31+G(d,p) level, applied to explain the structure-activity relationship. Dimers showed 2-2.5-fold higher values of k A than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant activity for monomers and dimers with α,β-unsaturated side chains. Curcumin and 6 in fact are dimers of the same monomer 2. We conclude that the type of linkage between the two "halves" by which the molecule is made up does not exert influence on the antioxidant efficiency and reactivity of these two dimers. The dimers and the monomers demonstrated higher activity than Trolox (10) in aqueous medium (model 3). A comparison of the studied compounds with DL-α-tocopherol (11), Trolox and curcumin is made. All dimers are characterized through lower bond dissociation enthalpies (BDEs) than their monomers (model 4), which qualitatively supports the experimental results.

  4. 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).

  5. Non-iterative method to calculate the periodical distribution of temperature in reactors with thermal regeneration

    International Nuclear Information System (INIS)

    Sanchez de Alsina, O.L.; Scaricabarozzi, R.A.

    1982-01-01

    A matrix non-iterative method to calculate the periodical distribution in reactors with thermal regeneration is presented. In case of exothermic reaction, a source term will be included. A computer code was developed to calculate the final temperature distribution in solids and in the outlet temperatures of the gases. The results obtained from ethane oxidation calculation in air, using the Dietrich kinetic data are presented. This method is more advantageous than iterative methods. (E.G.) [pt

  6. Gaussian elimination methods for calculating classical periodic trajectories in two dimensions

    International Nuclear Information System (INIS)

    Davies, K.T.R.

    1991-08-01

    A Gaussian-elimination method for calculating classical periodic trajectories is formulated for a two-dimensional system. Two variants of the theory are obtained, one assuming that the period of the motion is fixed and the other assuming that the total energy is fixed. Comparisons are made between various approaches. 14 refs

  7. 34 CFR 691.63 - Calculation of a grant for a payment period.

    Science.gov (United States)

    2010-07-01

    ... grade level progression. A student may not progress to the next year during a payment period. The... 34 Education 3 2010-07-01 2010-07-01 false Calculation of a grant for a payment period. 691.63... MATHEMATICS ACCESS TO RETAIN TALENT GRANT (NATIONAL SMART GRANT) PROGRAMS Determination of Awards § 691.63...

  8. 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.

  9. Development of a power-period calculation unit for nuclear reactor Control

    International Nuclear Information System (INIS)

    Martin, J.

    1966-10-01

    The apparatus studied is a digital calculating assembly which makes it possible to prepare and to present numerically the period and power of a nuclear reactor during operation, from start-up to nominal power. The pulses from a fission chamber are analyzed continuously, using real time. A small number of elements is required because of the systematic use of a calculation technique comprising the determination of a base 2 logarithm by a linear approximation. The accuracy obtained for the period is of the order of 14%; the response time of the order of the calculated period value. An approximate value of the power (30%) is given at each calculation cycle together with the power thresholds required for the control. (author) [fr

  10. Mössbauer spectroscopy and DFT calculations on all protonation states of the 2Fe-2S cluster of the Rieske protein

    Science.gov (United States)

    Müller, C. S.; Auerbach, H.; Stegmaier, K.; Wolny, J. A.; Schünemann, V.; Pierik, A. J.

    2017-11-01

    The Thermus thermophilus Rieske protein ( TtRP) contains a 2Fe-2S cluster with one iron (Fe-Cys) coordinated by four sulfur atoms (2xS2- and 2xCys) and one iron (Fe-His) by two sulfur and two nitrogen atoms (2xS2-, His134 and His154). Here, the protein is investigated at three pH values (6.0, 8.5 and 10.5) in order to elucidate the protonation states of the His-ligands. Examination of the effect of protonation on the electronic structure of the cluster via Mössbauer spectroscopy gives a deeper understanding of the coupling of electron transfer to the protonation state of the His-ligands. Two components (1 referring to Fe-Cys and 2 to Fe-His) with parameters typical for a diamagnetic [2Fe-2S]2+ cluster are detected. The Mössbauer parameters and the protonation state clearly correlate: while δ remains almost pH-independent with δ 1 (pH6.0) = 0.23 (± 0.01) mms- 1 and δ 1 (pH10.5) = 0.24 (± 0.01) mms- 1 for Fe-Cys, it decreases for Fe-His from δ 2 (pH6.0) = 0.34 (± 0.01) mms- 1 to δ 2 (pH10.5) = 0.28 (± 0.01) mms- 1. Δ E Q changes from Δ E Q1 (pH6.0) = 0.57 (± 0.01) mms- 1 to Δ E Q1 (pH10.5) = 0.45 (± 0.01) mms- 1 and from Δ E Q2 (pH6.0) = 1.05 (± 0.01) mms- 1 to Δ E Q2 (pH10.5) = 0.71 (± 0.01) mms- 1. Density functional theory (DFT)-calculations based on the crystal structure (pdb 1NYK) (Hunsicker-Wang et al. Biochemistry 42, 7303, 2003) have been performed for the Rieske-cluster with different His-ligand protonation states, reproducing the experimentally observed trend.

  11. Non-periodic pseudo-random numbers used in Monte Carlo calculations

    Science.gov (United States)

    Barberis, Gaston E.

    2007-09-01

    The generation of pseudo-random numbers is one of the interesting problems in Monte Carlo simulations, mostly because the common computer generators produce periodic numbers. We used simple pseudo-random numbers generated with the simplest chaotic system, the logistic map, with excellent results. The numbers generated in this way are non-periodic, which we demonstrated for 1013 numbers, and they are obtained in a deterministic way, which allows to repeat systematically any calculation. The Monte Carlo calculations are the ideal field to apply these numbers, and we did it for simple and more elaborated cases. Chemistry and Information Technology use this kind of simulations, and the application of this numbers to quantum Monte Carlo and cryptography is immediate. I present here the techniques to calculate, analyze and use these pseudo-random numbers, show that they lack periodicity up to 1013 numbers and that they are not correlated.

  12. Non-periodic pseudo-random numbers used in Monte Carlo calculations

    International Nuclear Information System (INIS)

    Barberis, Gaston E.

    2007-01-01

    The generation of pseudo-random numbers is one of the interesting problems in Monte Carlo simulations, mostly because the common computer generators produce periodic numbers. We used simple pseudo-random numbers generated with the simplest chaotic system, the logistic map, with excellent results. The numbers generated in this way are non-periodic, which we demonstrated for 10 13 numbers, and they are obtained in a deterministic way, which allows to repeat systematically any calculation. The Monte Carlo calculations are the ideal field to apply these numbers, and we did it for simple and more elaborated cases. Chemistry and Information Technology use this kind of simulations, and the application of this numbers to quantum Monte Carlo and cryptography is immediate. I present here the techniques to calculate, analyze and use these pseudo-random numbers, show that they lack periodicity up to 10 13 numbers and that they are not correlated

  13. Calculations of Changes in Reactivity during some regular periods of operation of JEN-1 MOD Reactor

    International Nuclear Information System (INIS)

    Alcala Ruiz, F.

    1973-01-01

    By a Point-Reactor model and Perturbation Theory, changes in reactivity during some regular operating periods of JEN-1 MOD Reactor have been calculated and compared with available measured values. they were in good agreement. Also changes in reactivity have been calculated during operations at higher power levels than the present one, concluding some practical consequences for the case of increasing the present power of this reactor. (Author)

  14. 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

  15. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin

    2014-08-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  16. Calculation of nonstationary gas-dynamic flows with periodic local supply of energy

    International Nuclear Information System (INIS)

    Mikhailova, N.V.; Myshetskaya, E.E.; Rakhimov, A.T.; Favorskii, A.P.

    The paper considers the motion of a flow of gas with local supply of energy periodic in time. Solution of the problem in one-dimensional formulation in the approximation of an ideal nonviscous non-heat-conducting gas is carried out by numerical methods. The possibility of emergence of the flow into a periodic regime is established and the rate of this process is calculated. The character of the periodic structure is investigated in dependence on the frequency of the superimposition of perturbations and the Mach number in unperturbed flow of the gas

  17. 34 CFR 686.22 - Calculation of a grant for a payment period.

    Science.gov (United States)

    2010-07-01

    ... 34 Education 3 2010-07-01 2010-07-01 false Calculation of a grant for a payment period. 686.22 Section 686.22 Education Regulations of the Offices of the Department of Education (Continued) OFFICE OF POSTSECONDARY EDUCATION, DEPARTMENT OF EDUCATION TEACHER EDUCATION ASSISTANCE FOR COLLEGE AND HIGHER EDUCATION...

  18. Generalized Bloch Theorem for Complex Periodic Potentials - A Powerful Application to Quantum Transport Calculations

    International Nuclear Information System (INIS)

    Zhang, Xiaoguang; Varga, Kalman; Pantelides, Sokrates T

    2007-01-01

    Band-theoretic methods with periodically repeated supercells have been a powerful approach for ground-state electronic structure calculations, but have not so far been adapted for quantum transport problems with open boundary conditions. Here we introduce a generalized Bloch theorem for complex periodic potentials and use a transfer-matrix formulation to cast the transmission probability in a scattering problem with open boundary conditions in terms of the complex wave vectors of a periodic system with absorbing layers, allowing a band technique for quantum transport calculations. The accuracy and utility of the method is demonstrated by the model problems of the transmission of an electron over a square barrier and the scattering of a phonon in an inhomogeneous nanowire. Application to the resistance of a twin boundary in nanocrystalline copper yields excellent agreement with recent experimental data

  19. Life time calculations for LCF loading combined with tensional hold periods

    International Nuclear Information System (INIS)

    Bocek, M.; Armas, A.; Piel, D.

    1983-01-01

    The life time in high amplitude strain cycling with tensional hold periods is analysed presuming that creep failure damage is life determining. The life fraction rule (LFR) is used to calculate the life time consumpted during the dwell period in strain controlled tests as well as during tensional hold time stress cycles. It follows from the present investigation that stress relaxation occurring during the strain hold periods plays the dominant influence upon the relationship between life and dwell time. For strong stress relaxation (e.g. high temperature) less damage is accumulated as compared to suppressed relaxation (low temperature). The damage in stress relaxation is calculated by means of the LFR and the results are compared to experiments conducted on Zircaloy-4 and the austenitic stainless stell Type AISI 304. From the very good agreement between both it is concluded that under the loading conditions considered, creep failure damage is the main life determining damage contribution. (orig.)

  20. A complete vibrational study on a potential environmental toxicant agent, the 3,3',4,4'-tetrachloroazobenzene combining the FTIR, FTRaman, UV-Visible and NMR spectroscopies with DFT calculations.

    Science.gov (United States)

    Castillo, María V; Pergomet, Jorgelina L; Carnavale, Gustavo A; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A

    2015-01-05

    In this study 3,3',4,4'-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G(*) and 6-311++G(**) basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated (1)H and (13)C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The npp(*) transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands. Copyright © 2014. Published by Elsevier B.V.

  1. 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.

  2. Dimethyl methylphosphonate adsorption and decomposition on MoO2 as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

    Science.gov (United States)

    Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena; Yu, Yi; Karslıoǧlu, Osman; Eichhorn, Bryan; Kuklja, Maija M.; Bluhm, Hendrik

    2018-04-01

    Organophosphonates range in their toxicity and are used as pesticides, herbicides, and chemical warfare agents (CWAs). Few laboratories are equipped to handle the most toxic molecules, thus simulants such as dimethyl methylphosphonate (DMMP), are used as a first step in studying adsorption and reactivity on materials. Benchmarked by combined experimental and theoretical studies of simulants, calculations offer an opportunity to understand how molecular interactions with a surface changes upon using a CWA. However, most calculations of DMMP and CWAs on surfaces are limited to adsorption studies on clusters of atoms, which may differ markedly from the behavior on bulk solid-state materials with extended surfaces. We have benchmarked our solid-state periodic calculations of DMMP adsorption and reactivity on MoO2 with ambient pressure x-ray photoelectron spectroscopy studies (APXPS). DMMP is found to interact strongly with a MoO2 film, a model system for the MoO x component in the ASZM-TEDA© gas filtration material. Density functional theory modeling of several adsorption and decomposition mechanisms assist the assignment of APXPS peaks. Our results show that some of the adsorbed DMMP decomposes, with all the products remaining on the surface. The rigorous calculations benchmarked with experiments pave a path to reliable and predictive theoretical studies of CWA interactions with surfaces.

  3. 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.

  4. Large-scale compensation of errors in pairwise-additive empirical force fields: comparison of AMBER intermolecular terms with rigorous DFT-SAPT calculations

    Czech Academy of Sciences Publication Activity Database

    Zgarbová, M.; Otyepka, M.; Šponer, Jiří; Hobza, P.; Jurečka, P.

    2010-01-01

    Roč. 12, č. 35 (2010), s. 10476-10493 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA203/09/1476 Grant - others:GA MŠk(CZ) LC512; GA MŠk(CZ) GD203/09/H046 Program:LC; GD Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : amber empirical potential * DFT-SAPT * compensation of errors Subject RIV: BO - Biophysics Impact factor: 3.454, year: 2010

  5. Highly efficient regioselective synthesis, spectroscopic characterizations and DFT calculations of novel hydroxymethylated 1,4-disubstituted-1,2,3-triazole-based sulfonamides

    Science.gov (United States)

    Taheri, Elmira; Mirjafary, Zohreh; Saeidian, Hamid

    2018-04-01

    The novel hydroxymethylated 1,4-disubstituted-1,2,3-triazole-based sulfonamides were synthesized in excellent yields and high regioselectivity via a one-pot, two-step, three-component reaction of N-propargylsulfonamides, sodium azide, and epoxide derivatives under green conditions. Green and mild reaction condition, commercially readily available and inexpensive starting materials, wide scope and easy work-up are the key features of the present method. The Li+ and Na+ ion affinities of the model structure have been also investigated by density functional theory (DFT) studies to find the applicability of these products as ligand in coordination chemistry.

  6. Rose-like I-doped Bi{sub 2}O{sub 2}CO{sub 3} microspheres with enhanced visible light response: DFT calculation, synthesis and photocatalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Zai, Jiantao; Cao, Fenglei; Liang, Na; Yu, Ke; Tian, Yuan; Sun, Huai; Qian, Xuefeng, E-mail: xfqian@sjtu.edu.cn

    2017-01-05

    Highlights: • DFT reveals I{sup −} can partially substitute CO{sub 3}{sup 2−}to narrow the bandgap of Bi{sub 2}O{sub 2}CO{sub 3}. • Sodium citrate play a key role on the formation of rose-like I-doped Bi{sub 2}O{sub 2}CO{sub 3}. • Rose-like I-doped Bi{sub 2}O{sub 2}CO{sub 3} show enhanced visible light response. • The catalyst has enhanced photocatalytic activity to organic and Cr(VI) pollutes. - Abstract: Based on the crystal structure and the DFT calculation of Bi{sub 2}O{sub 2}CO{sub 3}, I{sup −} can partly replace the CO{sub 3}{sup 2−}in Bi{sub 2}O{sub 2}CO{sub 3} to narrow its bandgap and to enhance its visible light absorption. With this in mind, rose-like I-doped Bi{sub 2}O{sub 2}CO{sub 3} microspheres were prepared via a hydrothermal process. This method can also be extended to synthesize rose-like Cl- or Br-doped Bi{sub 2}O{sub 2}CO{sub 3} microspheres. Photoelectrochemical test supports the DFT calculation result that I- doping narrows the bandgap of Bi{sub 2}O{sub 2}CO{sub 3} by forming two intermediate levels in its forbidden band. Further study reveals that I-doped Bi{sub 2}O{sub 2}CO{sub 3} microspheres with optimized composition exhibit the best photocatalytic activity. Rhodamine B can be completely degraded within 6 min and about 90% of Cr(VI) can be reduced after 25 min under the irradiation of visible light (λ > 400 nm).

  7. X-ray Single Crystal Structure, DFT Calculations and Biological Activity of 2-(3-Methyl-5-(pyridin-2’-yl-1H-pyrazol-1-yl Ethanol

    Directory of Open Access Journals (Sweden)

    Smaail Radi

    2016-08-01

    Full Text Available A pyridylpyrazole bearing a hydroxyethyl substituent group has been synthesized by condensation of (Z-4-hydroxy-4-(pyridin-2-ylbut-3-en-2-one with 2-hydroxyethylhydrazine. The compound was well characterized and its structure confirmed by single crystal X-ray diffraction. Density functional calculations have been performed using DFT method with 6-31G* basis set. The HOMO-LUMO energy gap, binding energies and electron deformation densities are calculated at the DFT (BLYP, PW91, PWC level. The electrophilic f(− and nucleophilic f(+ Fukui functions and also the electrophilic and nucleophilic Parr functions are well adapted to find the electrophile and nucleophile centers in the molecule. The title compound has been tested for its DPPH radical scavenging activity which is involved in aging processes, anti-inflammatory, anticancer and wound healing activity. Compound is also found with a significant antioxidant activity, probably due to the ability to donate a hydrogen atom to the DPPH radical.

  8. Application of the method of integral equations to calculating the electrodynamic characteristics of periodically corrugated waveguides

    International Nuclear Information System (INIS)

    Belov, V.E.; Rodygin, L.V.; Fil'chenko, S.E.; Yunakovskii, A.D.

    1988-01-01

    A method is described for calculating the electrodynamic characteristics of periodically corrugated waveguide systems. This method is based on representing the field as the solution of the Helmholtz vector equation in the form of a simple layer potential, transformed with the use of the Floquet conditions. Systems of compound integral equations based on a weighted vector function of the simple layer potential are derived for waveguides with azimuthally symmetric and helical corrugations. A numerical realization of the Fourier method is cited for seeking the dispersion relation of azimuthally symmetric waves of a circular corrugated waveguide

  9. 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.

  10. Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

    Science.gov (United States)

    Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

    2018-04-01

    Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

  11. 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.

  12. Temperature effects on prevalent structures of hydrated Fe{sup +} complexes: Infrared spectroscopy and DFT calculations of Fe{sup +}(H{sub 2}O){sub n} (n = 3–8)

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Kazuhiko, E-mail: kazu@chem.kyushu-univ.jp; Sekiya, Hiroshi [Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581 (Japan); Sasaki, Jun; Yamamoto, Gun [Department of Chemistry, Graduate School of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581 (Japan); Judai, Ken; Nishi, Nobuyuki [Institute for Molecular Science, Myodaiji, Okazaki 444-8585 (Japan)

    2014-12-07

    Hydrated Fe{sup +} ions are produced in a laser-vaporization cluster source of a triple quadrupole mass spectrometer. The Fe{sup +}(H{sub 2}O){sub n} (n = 3–8) complexes are mass-selected and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region. Density functional theory (DFT) calculations are also carried out for analyzing the experimental IR spectra and for evaluating thermodynamic quantities of low-lying isomers. Solvation through H-bonding instead of direct coordination to Fe{sup +} is observed already at n = 3, indicating the completion of the first hydration shell with two H{sub 2}O molecules. Size dependent variations in the spectra for n = 5–7 provide evidence for the second-shell completion at n = 6, where a linearly coordinated Fe{sup +}(H{sub 2}O){sub 2} subunit is solvated with four H{sub 2}O molecules. Overall spectral features for n = 3–8 agree well with those predicted for 2-coordinated structures. DFT calculations predict that such 2-coordinated structures are lowest in energy for smaller n. However, 4-coordinated isomers are predicted to be more stable for n = 7 and 8; the energy ordering is in conflict with the IR spectroscopic observation. Examination of free energy as a function of temperature suggests that the ordering of the isomers at warmer temperatures can be different from the ordering near 0 K. For n = 7 and 8, the 4-coordinated isomers should be observed at low temperatures because they are lowest in enthalpy. Meanwhile, outer-shell waters in the 2-coordinated structures are bound less rigidly; their contribution to entropy is rather large. The 2-coordinated structures become abundant at warmer temperatures, owing to the entropy effect.

  13. DFT calculations of strain and interface effects on electronic structures and magnetic properties of L10-FePt/Ag heterojunction of GMR applications

    Science.gov (United States)

    Pramchu, Sittichain; Jaroenjittichai, Atchara Punya; Laosiritaworn, Yongyut

    2018-03-01

    In this work, density functional theory (DFT) was employed to investigate the effect of strain and interface on electronic structures and magnetic properties of L10-FePt/Ag heterojunction. Two possible interface structures of L10-FePt(001)/Ag(001), that is, interface between Fe and Ag layers (Fe/Ag) and between Pt and Ag layers (Pt/Ag), were inspected. It was found that Pt/Ag interface is more stable than Fe/Ag interface due to its lower formation energy. Further, under the lattice mismatch induced tensile strain, the enhancement of magnetism for both Fe/Ag and Pt/Ag interface structures has been found to have progressed, though the magnetic moments of "interfacial" Fe and Pt atoms have been found to have decreased. To explain this further, the local density of states (LDOS) analysis suggests that interaction between Fe (Pt) and Ag near Fe/Ag (Pt/Ag) interface leads to spin symmetry breaking of the Ag atom and hence induces magnetism magnitude. In contrast, the magnetic moments of interfacial Fe and Pt atoms reduce because of the increase in the electronic states near the Fermi level of the minority-spin electrons. In addition, the significant enhancements of the LDOS near the Fermi levels of the minority-spin electrons signify the boosting of the transport properties of the minority-spin electrons and hence the spin-dependent electron transport at this ferromagnet/metal interface. From this work, it is expected that this clarification of the interfacial magnetism may inspire new innovation on how to improve spin-dependent electron transport for enhancing the giant magnetoresistance (GMR) ratio of potential GMR-based spintronic devices.

  14. DFT calculations of strain and interface effects on electronic structures and magnetic properties of L10-FePt/Ag heterojunction of GMR applications

    Directory of Open Access Journals (Sweden)

    Sittichain Pramchu

    2018-03-01

    Full Text Available In this work, density functional theory (DFT was employed to investigate the effect of strain and interface on electronic structures and magnetic properties of L10-FePt/Ag heterojunction. Two possible interface structures of L10-FePt(001/Ag(001, that is, interface between Fe and Ag layers (Fe/Ag and between Pt and Ag layers (Pt/Ag, were inspected. It was found that Pt/Ag interface is more stable than Fe/Ag interface due to its lower formation energy. Further, under the lattice mismatch induced tensile strain, the enhancement of magnetism for both Fe/Ag and Pt/Ag interface structures has been found to have progressed, though the magnetic moments of “interfacial” Fe and Pt atoms have been found to have decreased. To explain this further, the local density of states (LDOS analysis suggests that interaction between Fe (Pt and Ag near Fe/Ag (Pt/Ag interface leads to spin symmetry breaking of the Ag atom and hence induces magnetism magnitude. In contrast, the magnetic moments of interfacial Fe and Pt atoms reduce because of the increase in the electronic states near the Fermi level of the minority-spin electrons. In addition, the significant enhancements of the LDOS near the Fermi levels of the minority-spin electrons signify the boosting of the transport properties of the minority-spin electrons and hence the spin-dependent electron transport at this ferromagnet/metal interface. From this work, it is expected that this clarification of the interfacial magnetism may inspire new innovation on how to improve spin-dependent electron transport for enhancing the giant magnetoresistance (GMR ratio of potential GMR-based spintronic devices.

  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. Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

    Science.gov (United States)

    Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K; Chibotaru, Liviu F; Delcey, Mickaël G; De Vico, Luca; Fdez Galván, Ignacio; Ferré, Nicolas; Frutos, Luis Manuel; Gagliardi, Laura; Garavelli, Marco; Giussani, Angelo; Hoyer, Chad E; Li Manni, Giovanni; Lischka, Hans; Ma, Dongxia; Malmqvist, Per Åke; Müller, Thomas; Nenov, Artur; Olivucci, Massimo; Pedersen, Thomas Bondo; Peng, Daoling; Plasser, Felix; Pritchard, Ben; Reiher, Markus; Rivalta, Ivan; Schapiro, Igor; Segarra-Martí, Javier; Stenrup, Michael; Truhlar, Donald G; Ungur, Liviu; Valentini, Alessio; Vancoillie, Steven; Veryazov, Valera; Vysotskiy, Victor P; Weingart, Oliver; Zapata, Felipe; Lindh, Roland

    2016-02-15

    In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization. © 2015 Wiley Periodicals, Inc.

  17. 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.

  18. 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

  19. 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.

  20. New insights into the origin of visible-light photocatalytic activity in Se-modified anatase TiO2 from screened coulomb hybrid DFT calculations

    KAUST Repository

    Harb, Moussab

    2013-01-01

    ), TiO(2-x)Sex (containing Se2- species), and TiO(2-x)Se2x (containing Se2 2- species) reveal significant enhanced visible-light optical absorption spectra with new absorption features appearing at 500, 600, and 690 nm, respectively. Our calculated

  1. Evaluation of uncertainty of ideal-gas entropy and heat capacity calculations by density functional theory (DFT) for molecules containing symmetrical internal rotors

    Czech Academy of Sciences Publication Activity Database

    Červinka, C.; Fulem, Michal; Růžička, K.

    2013-01-01

    Roč. 58, č. 5 (2013), s. 1382-1390 ISSN 0021-9568 Institutional support: RVO:68378271 Keywords : chemical thermodynamic properties * ab-initio calculation * vapor-pressure * xylene isomerization * organic-compounds * hindered rotation * methyl-groups * vaporization Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.045, year: 2013

  2. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide using DFT-D calculations and {sup 13}C solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco, E-mail: jacco.vandestreek@sund.ku.dk [Department of Pharmacy, University of Copenhagen, Universitetsparken 2, Copenhagen DK-2100 (Denmark)

    2014-08-01

    The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 ▶). Acta Cryst. B66, 615–621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@ecule’s 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: N—H⋯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.

  3. Development of a power-period calculation unit for nuclear reactor Control; Etude et realisation d'un ensemble de calcul puissance periode pour le controle d'un reacteur nucleaire

    Energy Technology Data Exchange (ETDEWEB)

    Martin, J [Commissariat a l' Energie Atomique, Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)

    1966-10-01

    The apparatus studied is a digital calculating assembly which makes it possible to prepare and to present numerically the period and power of a nuclear reactor during operation, from start-up to nominal power. The pulses from a fission chamber are analyzed continuously, using real time. A small number of elements is required because of the systematic use of a calculation technique comprising the determination of a base 2 logarithm by a linear approximation. The accuracy obtained for the period is of the order of 14%; the response time of the order of the calculated period value. An approximate value of the power (30%) is given at each calculation cycle together with the power thresholds required for the control. (author) [French] L'appareil etudie est un ensemble de calcul digital permettant d'elaborer et d'afficher numeriquement la periode et la puissance, d'un reacteur nucleaire lors de son fonctionnement depuis le demarrage jusqu'a la puissance nominale. Il traite en temps reel, de facon continue, les impulsions en provenance d'une chambre de fission. Grace a l'utilisation systematique d'une technique de calcul, la determination d'un logarithme a base 2 par approximation lineaire, un nombre reduit d'elements est utilise. La precision obtenue sur la periode est de l'ordre de 14 pour cent, le temps de reponse de l'ordre de la valeur de la periode calculee. Un ordre de grandeur de la puissance (30 pour cent) est donne a chaque cycle de calcul ainsi que des seuils de puissance necessaires au controle. (auteur)

  4. A corrected NEGF + DFT approach for calculating electronic transport through molecular devices: Filling bound states and patching the non-equilibrium integration

    International Nuclear Information System (INIS)

    Li Rui; Zhang Jiaxing; Hou Shimin; Qian Zekan; Shen Ziyong; Zhao Xingyu; Xue Zengquan

    2007-01-01

    We discuss two problems in the conventional approach for studying charge transport in molecular electronic devices that is based on the non-equilibrium Green's function formalism and density functional theory, i.e., the bound states and the numerical integration of the non-equilibrium density matrix. A scheme of filling the bound states in the bias window and a method of patching the non-equilibrium integration are proposed, both of which are referred to as the non-equilibrium correction. The discussion is illustrated by means of calculations on a model system consisting of a 4,4 bipyridine molecule connected to two semi-infinite gold monatomic chains

  5. The atomic structure of protons and hydrides in Sm1.92Ca0.08Sn2O7-δ pyrochlore from DFT calculations and FTIR spectroscopy

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Eurenius, K. E. J.; Rossmeisl, Jan

    2012-01-01

    A combined density functional theory and Fourier transform infrared spectroscopy study of the structure and specific site preference of protons and hydrides in the pyrochlore Sm1.92Ca0.08Sn2O7-δ is presented. Two protonic sites of particular high stability are identified, both located on O(1......) oxygen atoms closely associated with a Ca dopant. Further, the unexpected presence of Ho hydride defects in undoped, oxygen deficient Sm2Sn2O7 is reported. Finally, the stretching frequencies and relative intensities for these and other sites are calculated. The main features of the Fourier transform...

  6. Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: Formulation, proof of concept, and a pilot implementation

    International Nuclear Information System (INIS)

    Mao, Yuezhi; Horn, Paul R.; Mardirossian, Narbe; Head-Gordon, Teresa; Skylaris, Chris-Kriton; Head-Gordon, Martin

    2016-01-01

    Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF (PC) approach with the same large target basis set produces <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF (PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.

  7. Elucidating adsorption mechanisms of phthalate esters upon carbon nanotubes/graphene and natural organic acid competitive effects in water by DFT and MD calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuang; Wang, Se; Chen, Min Dong; Xu, Defu [Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu KeyLaboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), School ofEnvironmental Science and Engineering, Nanjing University of Information Science and Technology, Nanjing (China); Tang, Lili [Jiangsu Environmental Monitoring Centre, Nanjing (China); Wang, Degao [Dept. of Environmental Science and Engineering, Dalian Maritime University, Dalian (China)

    2015-06-15

    Simulations at multiple levels were performed to investigate the aqueous adsorption of phthalate esters (PAEs) on carbon nanoparticles and to find the competitive effect of a low molecular weight natural organic acid (benzoic acid) on the adsorption process. Six PAEs of varying alkyl side chain lengths and three carbon-based nanomaterials including a single-walled carbon nanotube (SWNT), double-walled carbon nanotube (DWNT), and graphene (G) were studied. Results showed that the adsorption energies calculated using density functional theory increase with increasing length of the PAE alkyl chain. G exhibits higher adsorption capacity for the PAEs than SWNT and DWNT. The absolute adsorption energies of these systems also display a positive linear correlation with the hydrophobicity of the PAE molecules. Molecular dynamics simulations indicate that the presence of neutral/anionic benzoic acid in water alleviates the PAE adsorption. Furthermore, anionic benzoic acid exerts more impact on the PAE adsorption than the neutral form.

  8. The effect of the flexibility of hydrogen bonding network on low-frequency motions of amino acids. Evidence from Terahertz spectroscopy and DFT calculations

    Science.gov (United States)

    Li, Yin; Lukács, András; Bordács, Sándor; Móczár, János; Nyitrai, Miklós; Hebling, János

    2018-02-01

    Low-frequency modes of L-Asp and L-Asn were studied in the range from 0.1 to 3.0 THz using time-domain Terahertz spectroscopy and density functional theory calculation. The results show that PBE-D2 shows more success than BLYP-D2 in prediction of THz absorption spectra. To compare their low-frequency modes, we adopted ;vibrational character ID strips; proposed by Schmuttenmaer and coworkers [Journal of Physical Chemistry B, 117, 10444(2013)]. We found that the most intense THz absorption peaks of two compounds both involve severe distortion of their hydrogen bonding networks. Due to less rigid hydrogen bonding network in L-Asp, the side chain (carboxyl group) of L-Asp exhibits larger motions than that (carboxamide group) of L-Asn in low-frequency modes.

  9. DFT calculations of the charged states of N@C60 and Fe4 single molecule magnets investigated in tunneling spectroscopy

    Science.gov (United States)

    Nossa, Javier; Islam, Fhokrul; Canali, Carlo; Pederson, Mark

    2012-02-01

    For device applications of single molecule magnets (SMMs) in high-density information storage and quantum-state control it is essential that the magnetic properties of the molecules remain stable under the influence of metallic contacts or surface environment. Recent tunneling experiments [1, 2] on N@C60 and Fe4 SMM have shown that these molecules preserve their magnetic characteristics when they are used as the central island of single-electron transistors. Although quantum spin models have been used extensively to study theoretically tunneling spectroscopy of SMMs, it has been shown recently that the orbital degrees of freedom, which is absent in spin models, can significantly affect the tunneling conductance [3]. In this work we present first-principles calculations of the neutral and charged states of N@C60 and Fe4 SMMs, and discuss a strategy to include their properties into a theory of quantum transport. We also present results of the magnetic anisotropy for the different charge states of Fe4 and discuss their relevance for experiments [2] in the sequential tunneling and cotunnelling regimes. [4pt] [1]. N. Roch et al., Phys. Rev. B 83, 081407 (2011). [0pt] [2]. A.S. Zyazin et al., Nano Lett. 10, 3307 (2010). [0pt] [3]. L. Michalak et al., Phys. Rev. Lett. 104, 017202 (2010).

  10. Synthesis, characterization, MCD spectroscopy, and TD-DFT calculations of copper-metalated nonperipherally substituted octaoctyl derivatives of tetrabenzotriazaporphyrin, cis- and trans-tetrabenzodiazaporphyrin, tetrabenzomonoazaporphyrin, and tetrabenzoporphyrin.

    Science.gov (United States)

    Mack, John; Sosa-Vargas, Lydia; Coles, Simon J; Tizzard, Graham J; Chambrier, Isabelle; Cammidge, Andrew N; Cook, Michael J; Kobayashi, Nagao

    2012-12-03

    Synthesis of the title compounds has been achieved through refinement of a recently reported synthetic protocol whereby varying equivalents of MeMgBr are reacted with 1,4-dioctylphthalonitrile to produce mixtures favoring specific hybrid structures. The initially formed magnesium-metalated compounds are obtained as pure materials and include, for the first time, both isomers (cis and trans) of tetrabenzodiazaporphyrin. The compounds were demetalated to the metal-free analogues, which were then converted into the copper-metalated derivatives. The X-ray structure of the copper tetrabenzotriazaporphyrin derivative is reported. The metal-free and copper-metalated macrocycles exhibit columnar mesophase behavior, and it is found that the mesophase stability is unexpectedly reduced in the diazaporphyrin derivatives compared to the rest of the series. The results of time-dependent density functional theory calculations for the copper complexes are compared to the observed optical properties. Michl's perimeter model was used as a conceptual framework for analyzing the magnetic circular dichroism spectral data, which predicted and accounted for trends in the observed experimental spectra.

  11. NMR spectroscopic characterization and DFT calculations of zirconium(IV)-3,3'-Br2-BINOLate and related complexes used in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones.

    Science.gov (United States)

    Blay, Gonzalo; Cano, Joan; Cardona, Luz; Fernández, Isabel; Muñoz, M Carmen; Pedro, José R; Vila, Carlos

    2012-12-07

    Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br(2)-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti(IV) and a dimeric structure in the cases of Zr(IV) and Hf(IV). Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-(R)-3,3'-Br(2)-BINOL)(2)] where each binaphthol ligand acts as bridge between the metal centers (Novak's model) is more stable than the dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-O(t)Bu)(2)] where the tert-butoxide groups act as bridging ligands (Kobayashi's model). The scope of the Friedel-Crafts alkylation with regard to the indole structure has been studied. Finally a plausible mechanism for the Friedel-Crafts reaction and a stereomodel for the mode of action of the catalyst that explain the observed stereochemistry of the reaction products have been proposed.

  12. [Fe(F20 TPP)Cl]-catalyzed amination with arylamines and {[Fe(F20 TPP)(NAr)](PhI=NAr)} + . Intermediate assessed by high-resolution ESI-MS and DFT calculations.

    Science.gov (United States)

    Liu, Yungen; Chen, Guo-Qiang; Tse, Chun-Wai; Guan, Xianguo; Xu, Zheng-Jiang; Huang, Jie-Sheng; Che, Chi-Ming

    2015-01-01

    Amination of CH bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for CN bond formation, and the use of iminoiodinanes, or their in situ generated forms from 'PhI(OAc)2 +primary amides (such as sulfonamides, sulfamates, and carbamates)', as nitrogen sources for the amination reaction has been well documented. In this work, a 'metal catalyst+PhI(OAc)2 +primary arylamines' amination protocol has been developed using [Fe(F20 TPP)Cl] (H2 F20 TPP=meso-tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra- and intermolecular amination of sp(2) and sp(3) CH bonds (>27 examples), affording the amination products, including natural products such as rutaecarpine, in moderate-to-good yields. ESI-MS analysis and DFT calculations lend support for the involvement of {[Fe(F20 TPP)(NC6 H4 -p-NO2 )](PhI=NC6 H4 -p-NO2 )} + . intermediate in the catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis, structural characterization, thermal analysis, and DFT calculation of a novel zinc (II)-trifluoro-β-diketonate 3D supramolecular nano organic-inorganic compound with 1,3,5-triazine derivative

    Energy Technology Data Exchange (ETDEWEB)

    Mirtamizdoust, Babak, E-mail: babakm.tamizdoust@gmail.com [Department of Chemistry, Yasouj University, Yasouj, 75918-74831 (Iran, Islamic Republic of); Department of Chemistry, Faculty of Science, University of Qom, PO Box 37185-359, Qom, Islamic Republic of Iran (Iran, Islamic Republic of); Ghaedi, Mehrorang [Department of Chemistry, Yasouj University, Yasouj, 75918-74831 (Iran, Islamic Republic of); Hanifehpour, Younes, E-mail: y_hanifehpour@yu.ac.kr [School of Mechanical Engineering, WCU Nano Research Center, Yeungnam University, Gyongsan, 712-749 (Korea, Republic of); Mague, Joel T. [Department of Chemistry, Tulane University, New Orleans (United States); Joo, Sang Woo, E-mail: swjoo1@gmail.com [School of Mechanical Engineering, WCU Nano Research Center, Yeungnam University, Gyongsan, 712-749 (Korea, Republic of)

    2016-10-01

    A sonochemical method was used to synthesize a novel nano-structure of a zinc(II) organic-inorganic compound [Zn(dapt){sub 2}(ttfa){sub 2}] (1) [dapt = 2,4-diamino-6-phenyl-1,3,5-triazine and ttfa = 2-thenoyltrifluoroacetonate]. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analysis, and thermal analysis. The single-crystal X-ray structure shows that 1 is a discrete coordination compound. Strong intra- and intermolecular hydrogen bonds are observed in the structure with the latter forming chains of molecules running parallel to (110). The chains are further extended into a three-dimensional supramolecular structure by intermolecular C−F⋯π interactions between trifluoromethyl and triazine moieties. The coordination number of the zinc(II) ion is six (ZnN{sub 2}O{sub 4}), and the coordination sphere is tetragonally elongated octahedral. The structure of the title complex was optimized by DFT calculations. - Highlights: • A new zinc(II) 3D coordination supramolecular compound was synthesized. • Ultrasound synthesis of nano coordination compound have been reported. • The X-ray crystal structure of the compound is reported.

  14. Synthesis, DFT calculations, spectroscopic and photovoltaic of the novel N″, N‴-bis[(4,9-dimethoxy-5-oxo-5H-furo[3,2-g]chromen-6-yl)methylidene] thiocarbonohydrazide (BFCMT) and its photodiode application

    Science.gov (United States)

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

    2018-03-01

    Condensation reaction of 6-formylkhellin (1) with thiocarbohydrazide in 2:1 M ratio afforded the novel N″, N‴-bis [(4, 9-dimethoxy-5-oxo-5H-furo [3,2-g]chromen-6-yl) methylidene]thiocarbonohydrazide (BFCMT) and its electronic absorption spectrum was interpreted by TD-DFT calculations. The electronic transition is direct allowed with onset and fundamental energy gaps of 1.06 and 3.36 eV, respectively. The estimated optical constants were applied to evaluate the optical transition type as well as the effective optical parameters. The current density-voltage characteristics of BFCMT/p-Si heterojunction at 300 K in dark and under illumination of 100 mW/cm2 showed rectifying characteristics. The capacitance-voltage characteristic parameters under illumination showed a reduction in the built-in potential and increasing the active carrier concentration. The loaded J-V characteristics of BFCMT/p-Si heterojunction under illumination were investigated and showed a remarkable power conversion efficiency of 0.83% without consideration of the refection correction or losses from the upper electrode absorption.

  15. A triple-bridged azido-Cu(II) chain compound fine-tuned by mixed carboxylate/ethanol linkers displays slow-relaxation and ferromagnetic order: synthesis, crystal structure, magnetic properties and DFT calculations.

    Science.gov (United States)

    Liu, Xiangyu; Chen, Sanping; Grancha, Thais; Pardo, Emilio; Ke, Hongshan; Yin, Bing; Wei, Qing; Xie, Gang; Gao, Shengli

    2014-11-07

    A new azido-Cu(II) compound, [Cu(4-fba)(N3)(C2H5OH)] (4-fba = 4-fluorobenzoic acid) (1), has been synthesized and characterized. The X-ray crystal structure analysis demonstrates that only one crystallographically independent Cu(II) ion in the asymmetric unit of 1 exhibits a stretched octahedral geometry in which two azido N atoms and two carboxylic O atoms locate in the equatorial square, while two ethanol O atoms occupy the apical positions, forming a 1D Cu(II) chain with an alternating triple-bridge of EO-azido, syn,syn-carboxylate, and μ2-ethanol. The title compound consists of ferromagnetically interacting ferromagnetic chains, which exhibit ferromagnetic order (T(c) = 7.0 K). The strong ferromagnetic coupling between adjacent Cu(II) ions within each chain is due to the countercomplementarity of the super-exchange pathways, whereas the ferromagnetic interchain interactions--responsible for the long-range magnetic ordering--are most likely due to the presence of coordinated ethanol molecules establishing hydrogen bonds with neighboring chains. DFT calculations have been performed on compound 1 to offer a qualitative theoretical explanation of the magnetic behavior.

  16. 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.

  17. Mechanism of phosphorus passivation of near-interface oxide traps in 4H–SiC MOS devices investigated by CCDLTS and DFT calculation

    Science.gov (United States)

    Jayawardena, Asanka; Shen, X.; Mooney, P. M.; Dhar, Sarit

    2018-06-01

    Interfacial charge trapping in 4H–SiC MOS capacitors with P doped SiO2 or phospho-silicate glass (PSG) as a gate dielectric has been investigated with temperature dependent capacitance–voltage measurements and constant capacitance deep level transient spectroscopy (CCDLTS) measurements. The measurements indicate that P doping in the dielectric results in significant reduction of near-interface electron traps that have energy levels within 0.5 eV of the 4H–SiC conduction band edge. Extracted trap densities confirm that the phosphorus induced near-interface trap reduction is significantly more effective than interfacial nitridation, which is typically used for 4H–SiC MOSFET processing. The CCDLTS measurements reveal that the two broad near-interface trap peaks, named ‘O1’ and ‘O2’, with activation energies around 0.15 eV and 0.4 eV below the 4H–SiC conduction band that are typically observed in thermal oxides on 4H–SiC, are also present in PSG devices. Previous atomic scale ab initio calculations suggested these O1 and O2 traps to be carbon dimers substituted for oxygen dimers (CO=CO) and interstitial Si (Sii) in SiO2, respectively. Theoretical considerations in this work suggest that the presence of P in the near-interfacial region reduces the stability of the CO=CO defects and reduces the density of Sii defects through the network restructuring. Qualitative comparison of results in this work and reported work suggest that the O1 and O2 traps in SiO2/4H–SiC MOS system negatively impact channel mobility in 4H–SiC MOSFETs.

  18. Calculation of the mean differential group delay of periodically spun, randomly birefringent fibers

    Science.gov (United States)

    Galtarossa, Andrea; Griggio, Paola; Pizzinat, Anna; Palmieri, Luca

    2002-05-01

    Spinning is one of the most effective and well-known ways to reduce polarization mode dispersion of optical fibers. In spite of the popularity of spinning, a detailed theory of spin effects is still lacking. We report an analytical expression for the mean differential group delay of a randomly birefringent spun fiber. The result holds for any periodic spin function with a period shorter than the fiber's beat length.

  19. An ab initio and TD DFT

    Indian Academy of Sciences (India)

    The photophysical behaviour of N-(2-hydroxy benzylidene) aniline or most commonly known as salicylideneaniline (SA) has been investigated using the ab initio and DFT levels of theory. The quantum chemical calculations show that the optimized non planar enol (1) form of the SA molecule is the most stable conformer ...

  20. Adsorption of F{sub 2}C=CFCl on TiO{sub 2} nano-powder: Structures, energetics and vibrational properties from DRIFT spectroscopy and periodic quantum chemical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Tasinato, Nicola, E-mail: tasinato@unive.it; Moro, Daniele; Stoppa, Paolo; Pietropolli Charmet, Andrea; Toninello, Piero; Giorgianni, Santi

    2015-10-30

    Graphical abstract: - Highlights: • Adsorption of F{sub 2}C=CFCl on TiO{sub 2} unveiled by DRIFTS and periodic DFT. • Structural, energetic and vibrational properties of F{sub 2}C=CFCl @ anatase (1 0 1). • Binding energies (B3LYP-D2) between −17 and −46 kJ mol{sup −1} depending on the anchor point. • Theory and experiment converge on the CF{sub 2} moiety as the main anchor point. - Abstract: Photodegradation over titanium dioxide (TiO{sub 2}) is a very appealing technology for removing environmental pollutants from the air, the adsorption interaction being the first step of the whole reaction pathway. In the present work the adsorption of F{sub 2}C=CFCl (chlorotrifluoroethene, halon 1113), a compound used by industry and detected in the atmosphere, on a commercial TiO{sub 2} nano-powder is investigated experimentally by in situ DRIFT spectroscopy and theoretically through periodic ab initio calculations rooted in DFT. The spectra of the adsorbed molecule suggest that the anchoring to the surface mainly takes place through F atoms. Theoretically, five adsorption configurations for the molecule interacting with the anatase (1 0 1) surface are simulated at B3LYP level and for each of them, structures, binding energies and vibrational frequencies are derived. The interplay between theory and experiments shows the coexistence of different adsorption configurations, the foremost ones featuring the interaction of one F atom with a fivefold coordinated Ti{sup 4+} of the surface. These two adsorption models, which mostly differ for the orientation of the adsorbate with respect to the surface, feature a binding energy of −45.6 and −41.0 kJ mol{sup −1} according to dispersion corrected DFT calculations. The favorable adsorption interaction appears as an important requirement toward the application of titanium dioxide technologies for the photocatalytic degradation of halon 1113.

  1. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev’s Periodic Table — Ele- ment No. 155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in or- der to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  2. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev's Periodic Table - Element No.155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in order to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  3. A structural study of [CpM(CO)3H] (M = Cr, Mo and W) by single-crystal X-ray diffraction and DFT calculations: sterically crowded yet surprisingly flexible molecules.

    Science.gov (United States)

    Burchell, Richard P L; Sirsch, Peter; Decken, Andreas; McGrady, G Sean

    2009-08-14

    The single-crystal X-ray structures of the complexes [CpCr(CO)3H] 1, [CpMo(CO)3H] 2 and [CpW(CO)3H] 3 are reported. The results indicate that 1 adopts a structure close to a distorted three-legged piano stool geometry, whereas a conventional four-legged piano stool arrangement is observed for 2 and 3. Further insight into the equilibrium geometries and potential energy surfaces of all three complexes was obtained by DFT calculations. These show that in the gas phase complex 1 also prefers a geometry close to a four-legged piano stool in line with its heavier congeners, and implying strong packing forces at work for 1 in the solid state. Comparison with their isolelectronic group 7 tricarbonyl counterparts [CpM(CO)3] (M = Mn 4 and Re 5) illustrates that 1, 2 and 3 are sterically crowded complexes. However, a surprisingly soft bending potential is evident for the M-H moiety, whose order (1 approximately = 2 < 3) correlates with the M-H bond strength rather than with the degree of congestion at the metal centre, indicating electronic rather than steric control of the potential. The calculations also reveal cooperative motions of the hydride and carbonyl ligands in the M(CO)3H unit, which allow the M-H moiety to move freely, in spite of the closeness of the four basal ligands, helping to explain the surprising flexibility of the crowded coordination sphere observed for this family of high CN complexes.

  4. Using Floquet periodicity to easily calculate dispersion curves and wave structures of homogeneous waveguides

    Science.gov (United States)

    Hakoda, Christopher; Rose, Joseph; Shokouhi, Parisa; Lissenden, Clifford

    2018-04-01

    Dispersion curves are essential to any guided-wave-related project. The Semi-Analytical Finite Element (SAFE) method has become the conventional way to compute dispersion curves for homogeneous waveguides. However, only recently has a general SAFE formulation for commercial and open-source software become available, meaning that until now SAFE analyses have been variable and more time consuming than desirable. Likewise, the Floquet boundary conditions enable analysis of waveguides with periodicity and have been an integral part of the development of metamaterials. In fact, we have found the use of Floquet boundary conditions to be an extremely powerful tool for homogeneous waveguides, too. The nuances of using periodic boundary conditions for homogeneous waveguides that do not exhibit periodicity are discussed. Comparisons between this method and SAFE are made for selected homogeneous waveguide applications. The COMSOL Multiphysics software is used for the results shown, but any standard finite element software that can implement Floquet periodicity (user-defined or built-in) should suffice. Finally, we identify a number of complex waveguides for which dispersion curves can be found with relative ease by using the periodicity inherent to the Floquet boundary conditions.

  5. A DFT + DMFT approach for nanosystems

    Energy Technology Data Exchange (ETDEWEB)

    Turkowski, Volodymyr; Kabir, Alamgir; Nayyar, Neha; Rahman, Talat S, E-mail: vturkows@mail.ucf.ed [Department of Physics, University of Central Florida, Orlando, FL 32816 (United States)

    2010-11-24

    We propose a combined density-functional-theory-dynamical-mean-field-theory (DFT + DMFT) approach for reliable inclusion of electron-electron correlation effects in nanosystems. Compared with the widely used DFT + U approach, this method has several advantages, the most important of which is that it takes into account dynamical correlation effects. The formalism is illustrated through different calculations of the magnetic properties of a set of small iron clusters (number of atoms 2 {<=} N {<=} 5). It is shown that the inclusion of dynamical effects leads to a reduction in the cluster magnetization (as compared to results from DFT + U) and that, even for such small clusters, the magnetization values agree well with experimental estimations. These results justify confidence in the ability of the method to accurately describe the magnetic properties of clusters of interest to nanoscience. (fast track communication)

  6. A DFT + DMFT approach for nanosystems

    International Nuclear Information System (INIS)

    Turkowski, Volodymyr; Kabir, Alamgir; Nayyar, Neha; Rahman, Talat S

    2010-01-01

    We propose a combined density-functional-theory-dynamical-mean-field-theory (DFT + DMFT) approach for reliable inclusion of electron-electron correlation effects in nanosystems. Compared with the widely used DFT + U approach, this method has several advantages, the most important of which is that it takes into account dynamical correlation effects. The formalism is illustrated through different calculations of the magnetic properties of a set of small iron clusters (number of atoms 2 ≤ N ≤ 5). It is shown that the inclusion of dynamical effects leads to a reduction in the cluster magnetization (as compared to results from DFT + U) and that, even for such small clusters, the magnetization values agree well with experimental estimations. These results justify confidence in the ability of the method to accurately describe the magnetic properties of clusters of interest to nanoscience. (fast track communication)

  7. The calculation of collective energies from periodic time-dependent Hartree-Fock solutions

    International Nuclear Information System (INIS)

    Zahed, I.; Baranger, M.

    1983-06-01

    A periodic TDHF solution is used as the reference state for a diagrammatic expansion of the propagator. A discrete Fourier transform leads to a function of energy, whose poles are the corresponding energy levels. Limiting the expansion to first-order diagrams leads to a new derivation of the Bohr-Sommerfeld-like quantization rule for collective states

  8. 20 CFR 1002.267 - How is compensation during the period of service calculated in order to determine the employee's...

    Science.gov (United States)

    2010-04-01

    ... 20 Employees' Benefits 3 2010-04-01 2010-04-01 false How is compensation during the period of service calculated in order to determine the employee's pension benefits, if benefits are based on compensation? 1002.267 Section 1002.267 Employees' Benefits OFFICE OF THE ASSISTANT SECRETARY FOR VETERANS' EMPLOYMENT AND TRAINING SERVICE, DEPARTMENT OF...

  9. Calculating residual flows through a multiple-inlet system: the conundrum of the tidal period

    Science.gov (United States)

    Duran-Matute, Matias; Gerkema, Theo

    2015-11-01

    The concept of residual, i.e., tidally-averaged, flows through a multiple inlet system is reappraised. The evaluation of the residual through-flow depends on the time interval over which is integrated, in other words, on how one defines the tidal period. It is demonstrated that this definition is ambiguous and that different definitions (based on, e.g., high waters, slack tides, etc.) yield very different results for the residual, also in terms of their long-term statistical properties (median and standard deviation). A basin-wide applicable method of defining the tidal period, in terms of enclosed water volume, is analyzed. We compare the different methods on the basis of high-resolution model results for the Western Dutch Wadden Sea. The multitude of tidal constituents together with wind variability creates broad distributions for the residuals, with standard deviations much larger than the mean or median residual flows.

  10. Magnetoresistance calculations for a two-dimensional electron gas with unilateral short-period strong modulation

    Czech Academy of Sciences Publication Activity Database

    Výborný, Karel; Smrčka, Ludvík

    2002-01-01

    Roč. 66, č. 20 (2002), s. 205318-1 - 205318-8 ISSN 0163-1829 R&D Projects: GA ČR GA202/01/0754 Institutional research plan: CEZ:AV0Z1010914 Keywords : magnetoresistance * short-period superlattices * two-dimensional electron gas Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.327, year: 2002

  11. Redox Potentials of Ligands and Complexes – a DFT Approach

    African Journals Online (AJOL)

    NICO

    Electron affinity (EA) of an atom or molecule is the associated energy change that occurs .... As a consequence of the foregoing evidence we resolved to embark on a ... Density functional theory (DFT) calculations were performed using the ...

  12. A density functional theory (DFT) calculation

    Indian Academy of Sciences (India)

    Acid-base properties of drugs are important in understanding the behaviour of these compounds under physiological condition. In order to understand such behaviour the proton affinities of acridine 4-carboxamides with substitution (R) at the 9-position are theoretically studied, and considered for the basic sites of both the ...

  13. 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.

  14. Periodic subsystem density-functional theory

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2014-01-01

    By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed

  15. Periodic subsystem density-functional theory

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2014-11-01

    By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn-Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn-Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.

  16. The MSINDO-sCIS and MSINDO-UCIS methods. Procedures for the calculation of properties of excited states in molecules and periodic systems by a semiempirical approach

    International Nuclear Information System (INIS)

    Gadaczek, Immanuel Patrick

    2013-01-01

    Theoretical background, parameterization and performance of the newly developed semiempirical configuration interaction singles (CIS) method MSINDO-sCIS (scaled configuration interaction singles) are presented. The CIS Hamiltonian is modified by scaling of the Coulomb and exchange integrals and a semiempirical correction of the diagonal elements. For a recently proposed benchmark set of 28 medium-sized organic molecules, vertical excitation energies for singlet and triplet states have been calculated and statistically evaluated. A full reparameterization of the MSINDO method for both ground and excited state properties was performed. The results of the reparameterized MSINDO-sCIS method are compared to the currently best semiempirical method for excited states, OM3-CISDTQ by Thiel et al., and to other standard methods, such as time-dependent density- functional theory. The mean absolute deviation with respect to the theoretical best estimates (TBEs) for MSINDO-sCIS is 0.44 eV, comparable to the OM3 method but significantly smaller than for Zerner's INDO/S. The computational effort is strongly reduced compared to OM3-CISDTQ and OM3-MRCISD, since only single excitations are taken into account. Higher excitations are implicitly included by parameterization and the empirical correction term. By application of the Davidson-Liu block diagonalization method high computational efficiency is achieved. Furthermore it is demonstrated, that the MSINDO-sCIS method correctly describes charge-transfer (CT) states, that represent a crucial problem for time-dependent density functional theory (TD-DFT) methods. Additionally this method is extended to open-shell systems by the UCIS (unrestricted CIS) approach. MSINDO allows the calculation of periodic systems via the cyclic cluster model (CCM) which is a direct-space approach and therefore can be in principle combined with all molecular quantum-chemical techniques. The sCIS/UCIS equations are solved for a cluster with periodic

  17. Configuration space Faddeev calculations: Progress report for period 1 January 1986-31 December 1986

    International Nuclear Information System (INIS)

    Payne, G.L.; Klink, W.H.; Polyzou, W.N.

    1987-01-01

    The detailed study of few-body nuclear systems provides a powerful tool to identify the relevant degrees of freedom in the nucleus. For these systems one can perform detailed and accurate numerical calculations which can be used to study the interactions between the various degrees of freedom. We have used these systems to investigate the size of the relativistic effects, the role of meson exchange currents, and the importance of the quark degrees of freedom in the nuclear system. New computational tools have been developed to treat relativistic operators. The effects of the Coulomb polarization potential on the low-energy scattering parameters have been investigated, and the effects of the Coulomb interaction on charge symmetry breaking have been studied. We have continued our project to find representations for multiparticle scattering amplitudes which satisfy certain physical properties. Finally, we have extended our work on the realization of the irreducible representations of compact groups as spaces of polynomials. These realizations can then be used in a symbolic manipulation program to generate Clebsch-Gordan and Racah coefficients for groups important in nuclear physics applications. 37 refs

  18. Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy. Evidence for the generation of a cobalt-N2O complex. Experimental and DFT calculations.

    Science.gov (United States)

    Chacón Villalba, M Elizabeth; Franca, Carlos A; Güida, Jorge A

    2017-04-05

    The solid state photolysis of sodium, silver and thallium hyponitrite (M 2 N 2 O 2 , M=Na, Ag, Tl) salts and a binuclear complex of cobalt bridged by hyponitrite ([Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ ) were studied by irradiation with visible and UV light in the electronic absorption region. The UV-visible spectra for free hyponitrite ion and binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order to explain photolysis behavior. The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with 340-460nm light and with the 488nm laser line generates photolysis only in silver and thallium hyponitrite salts, while 253.7nm light photolyzed all the studied compounds. Infrared spectroscopy was used to follow the photolysis process and to identify the generated products. Remarkably, gaseous N 2 O was detected after photolysis in the infrared spectra of sodium, silver, and thallium hyponitrite KBr pellets. The spectra for [Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ suggest that one cobalt ion remains bonded to N 2 O from which the generation of a [(NH 3 ) 5 CoNNO] +3 complex is inferred. Density Functional Theory (DFT) based calculations confirm the stability of this last complex and provide the theoretical data which are used in the interpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elucidation of their photolysis behavior. Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmospheric CO 2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of the binuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the intensity increase in the N 2 O generation. Predicted and experimental data are in very good agreement. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Unprecedented .pi. ... .pi. interaction between an aromatic ring and a pseudo-aromatic ring formed through intramolecular H-bonding in a bidentate Schiff base ligand: crystal structure and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Dutta, A.; Jana, A. D.; Gangopadhyay, S.; Das, K. K.; Marek, J.; Marek, R.; Brus, Jiří; Ali, M.

    2011-01-01

    Roč. 13, č. 35 (2011), s. 15845-15853 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40500505 Keywords : X-Ray diffraction * ss-NMR * DFT Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.573, year: 2011

  20. Identifying systematic DFT errors in catalytic reactions

    DEFF Research Database (Denmark)

    Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Using CO2 reduction reactions as examples, we present a widely applicable method for identifying the main source of errors in density functional theory (DFT) calculations. The method has broad applications for error correction in DFT calculations in general, as it relies on the dependence...... of the applied exchange–correlation functional on the reaction energies rather than on errors versus the experimental data. As a result, improved energy corrections can now be determined for both gas phase and adsorbed reaction species, particularly interesting within heterogeneous catalysis. We show...... that for the CO2 reduction reactions, the main source of error is associated with the C[double bond, length as m-dash]O bonds and not the typically energy corrected OCO backbone....

  1. Nonempirical electron-correlation calculations on ALik and Alik+1+ clusters formed with elements from the second and third periods

    International Nuclear Information System (INIS)

    Mebel', A.M.; Klimenko, N.M.; Charkin, O.P.

    1988-01-01

    Several basic sets have been used (from 3-21 G A * to DZHD + P A ) with electron correlation in the Meller-Plesset MP3 approximation in nonempirical calculations on ALi k+1 + and ALi K+1 + lithium clusters (CLi 2 , CLi 3 + , NLi 3 , NLi 4 + , OLi 2 , OLi 3 + , etc.) formed with elements from the second and third periods in the lowest singlet states. A study has been made on the effects of the approximation on the results. Several reference systems are used to show that the SCF/3-21G A * approximation describes the lithide geometry satisfactorily, while MP3/DZHD + P A gives a satisfactory description of the affinity of Ali k for Li + . These approximations have been taken as optimal for calculations on the other compounds. The Li + affinities are highest for NLi 3 and PLi 3 (90 and 84 kcal correspondingly) and decrease as A varies along the subgroups from the second to the third and the lower sp periods, as well as when A varies in each period from the middle to the start or end. The affinities of the analogous compounds for Na + are less by 5-10 kcal than those for Li + . The values are compared with the proton affinities for the related hydrides AK k

  2. A DFT-D study of structural and energetic properties of TiO2 modifications

    International Nuclear Information System (INIS)

    Moellmann, Jonas; Ehrlich, Stephan; Tonner, Ralf; Grimme, Stefan

    2012-01-01

    The structures and relative energies of the three naturally occurring modifications of titanium dioxide (rutile, brookite and anatase) were investigated. For an accurate description, atom-pairwise dispersion-corrected density functional theory (DFT-D) was applied. The DFT-D3 scheme was extended non-empirically to improve the description of Ti atoms in bulk systems. New dispersion coefficients were derived from TDDFT calculations for electrostatically embedded TiO 2 clusters. The dispersion coefficient C 6 TiTi is reduced by a factor of 18 compared to the free atom. The three TiO 2 modifications were optimized in periodic plane-wave calculations with dispersion-corrected GGA (PBE, revPBE) and hybrid density functionals (PBE0, revPBE0). The calculated lattice parameters are in good agreement with experimental data, in particular the dispersion-corrected PBE0 and revPBE0 hybrid functionals. Although the observed relative stabilities could not be reproduced in all cases, dispersion corrections improve the results. For an accurate description of bulk metal oxides, London dispersion is a prominent force that should not be neglected when energies and structures are computed with DFT. Additionally, the influence of dispersion interactions on the relaxation of the TiO 2 (110) surface is investigated.

  3. A suggested periodic table up to Z≤ 172, based on Dirac-Fock calculations on atoms and ions.

    Science.gov (United States)

    Pyykkö, Pekka

    2011-01-07

    Extended Average Level (EAL) Dirac-Fock calculations on atoms and ions agree with earlier work in that a rough shell-filling order for the elements 119-172 is 8s Periodic Table develops further that of Fricke, Greiner and Waber [Theor. Chim. Acta 1971, 21, 235] by formally assigning the elements 121-164 to (nlj) slots on the basis of the electron configurations of their ions. Simple estimates are made for likely maximum oxidation states, i, of these elements M in their MX(i) compounds, such as i = 6 for UF(6). Particularly high i are predicted for the 6f elements.

  4. Combined spectroscopic, DFT, TD-DFT and MD study of newly synthesized thiourea derivative

    Science.gov (United States)

    Menon, Vidya V.; Sheena Mary, Y.; Shyma Mary, Y.; Panicker, C. Yohannan; Bielenica, Anna; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, Christian

    2018-03-01

    A novel thiourea derivative, 1-(3-bromophenyl)-3-[3-(trifluoromethyl)phenyl]thiourea (ANF-22) is synthesized and characterized by FTIR, FT-Raman and NMR spectroscopy experimentally and theoretically. A detailed conformational analysis of the title molecule has been conducted in order to locate the lowest energy geometry, which was further subjected to the detailed investigation of spectroscopic, reactive, degradation and docking studies by density functional theory (DFT) calculations and molecular dynamics (MD) simulations. Time dependent DFT (TD-DFT) calculations have been used also in order to simulate UV spectra and investigate charge transfer within molecule. Natural bond orbital analysis has been performed analyzing the charge delocalization and using HOMO and LUMO energies the electronic properties are analyzed. Molecular electrostatic potential map is used for the quantitative measurement of active sites in the molecule. In order to determine the locations possibly prone to electrophilic attacks we have calculated average local ionization energies and mapped them to the electron density surface. Further insight into the local reactivity properties have been obtained by calculation of Fukui functions, also mapped to the electron density surface. Possible degradation properties by the autoxidation mechanism have been assessed by calculations of bond dissociation energies for hydrogen abstraction. Atoms of title molecule with significant interactions with water molecules have been determined by calculations of radial distribution functions. The title compound can be a lead compound for developing new analgesic drug.

  5. Generalized gravity from modified DFT

    International Nuclear Information System (INIS)

    Sakatani, Yuho; Uehara, Shozo; Yoshida, Kentaroh

    2017-01-01

    Recently, generalized equations of type IIB supergravity have been derived from the requirement of classical kappa-symmetry of type IIB superstring theory in the Green-Schwarz formulation. These equations are covariant under generalized T-duality transformations and hence one may expect a formulation similar to double field theory (DFT). In this paper, we consider a modification of the DFT equations of motion by relaxing a condition for the generalized covariant derivative with an extra generalized vector. In this modified double field theory (mDFT), we show that the flatness condition of the modified generalized Ricci tensor leads to the NS-NS part of the generalized equations of type IIB supergravity. In particular, the extra vector fields appearing in the generalized equations correspond to the extra generalized vector in mDFT. We also discuss duality symmetries and a modification of the string charge in mDFT.

  6. Generalized gravity from modified DFT

    Energy Technology Data Exchange (ETDEWEB)

    Sakatani, Yuho [Department of Physics, Kyoto Prefectural University of Medicine,Kyoto 606-0823 (Japan); Fields, Gravity and Strings, CTPU,Institute for Basic Sciences, Daejeon 34047 (Korea, Republic of); Uehara, Shozo [Department of Physics, Kyoto Prefectural University of Medicine,Kyoto 606-0823 (Japan); Yoshida, Kentaroh [Department of Physics, Kyoto University,Kitashirakawa Oiwake-cho, Kyoto 606-8502 (Japan)

    2017-04-20

    Recently, generalized equations of type IIB supergravity have been derived from the requirement of classical kappa-symmetry of type IIB superstring theory in the Green-Schwarz formulation. These equations are covariant under generalized T-duality transformations and hence one may expect a formulation similar to double field theory (DFT). In this paper, we consider a modification of the DFT equations of motion by relaxing a condition for the generalized covariant derivative with an extra generalized vector. In this modified double field theory (mDFT), we show that the flatness condition of the modified generalized Ricci tensor leads to the NS-NS part of the generalized equations of type IIB supergravity. In particular, the extra vector fields appearing in the generalized equations correspond to the extra generalized vector in mDFT. We also discuss duality symmetries and a modification of the string charge in mDFT.

  7. Thinking soap But Speaking ‘oaps’. The Sound Preparation Period: Backward Calculation From Utterance to Muscle Innervation

    Directory of Open Access Journals (Sweden)

    Nora Wiedenmann

    2010-04-01

    Full Text Available

    In this article’s model—on speech and on speech errors, dyscoordinations, and disorders—, the time-course from the muscle innervation impetuses to the utterance of sounds as intended for canonical speech sound sequences is calculated backward. This time-course is shown as the sum of all the known physiological durations of speech sounds and speech gestures that are necessary to produce an utterance. The model introduces two internal clocks, based on positive or negative factors, representing certain physiologically-based time-courses during the sound preparation period (Lautvorspann. The use of these internal clocks show that speech gestures—like other motor activities—work according to a simple serialization principle: Under non-default conditions,
    alterations of the time-courses may cause speech errors of sound serialization, dyscoordinations of sounds as observed during first language acquisition, or speech disorders as pathological cases. These alterations of the time-course are modelled by varying the two internal-clock factors. The calculation of time-courses uses as default values the sound durations of the context-dependent Munich PHONDAT Database of Spoken German (see Appendix 4. As a new, human approach, this calculation agrees mathematically with the approach of Linear Programming / Operations Research. This work gives strong support to the fairly old suspicion (of 1908 of the famous Austrian speech error scientist Meringer [15], namely that one mostly thinks and articulates in a different serialization than is audible from one’s uttered sound sequences.

  8. 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.

  9. Wannier-function-based constrained DFT with nonorthogonality-correcting Pulay forces in application to the reorganization effects in graphene-adsorbed pentacene

    Science.gov (United States)

    Roychoudhury, Subhayan; O'Regan, David D.; Sanvito, Stefano

    2018-05-01

    Pulay terms arise in the Hellmann-Feynman forces in electronic-structure calculations when one employs a basis set made of localized orbitals that move with their host atoms. If the total energy of the system depends on a subspace population defined in terms of the localized orbitals across multiple atoms, then unconventional Pulay terms will emerge due to the variation of the orbital nonorthogonality with ionic translation. Here, we derive the required exact expressions for such terms, which cannot be eliminated by orbital orthonormalization. We have implemented these corrected ionic forces within the linear-scaling density functional theory (DFT) package onetep, and we have used constrained DFT to calculate the reorganization energy of a pentacene molecule adsorbed on a graphene flake. The calculations are performed by including ensemble DFT, corrections for periodic boundary conditions, and empirical Van der Waals interactions. For this system we find that tensorially invariant population analysis yields an adsorbate subspace population that is very close to integer-valued when based upon nonorthogonal Wannier functions, and also but less precisely so when using pseudoatomic functions. Thus, orbitals can provide a very effective population analysis for constrained DFT. Our calculations show that the reorganization energy of the adsorbed pentacene is typically lower than that of pentacene in the gas phase. We attribute this effect to steric hindrance.

  10. The Conceptual Model of Calculating the Return Period of the Costs for Creation of the Enterprise’s Economic Security Service in the Short-Term Period

    Directory of Open Access Journals (Sweden)

    Melikhova Tetiana O.

    2018-03-01

    Full Text Available Determination of the return period of the costs, advanced for the creation of economic security service of enterprise during a year, involves consideration of interaction of the conditional money flow, accumulated for a certain number of months, and the constant costs. The main component of the constant costs are the annual depreciation deductions. The return period is considered as gross, net, valid, and specified. The gross (net, valid, and specified return period is the time, wherein the gross conditional money flow, equal to the advanced costs, will be accumulated. The gross return period, taking account of the effect of time factor, is proposed to be defined as the ratio of annual depreciation deductions increased by the annual compounding coefficient to the conditional average monthly gross money flow, increased by the average monthly inflation index. As for the short-term period, a relationship between the gross, net, valid, and specified return periods of the costs, advanced to the creation of the economic security service, has been identified. The net (valid, specified return period is equal to the gross period adjusted to the coefficient of excess of the gross conditional money flow, accumulated in the gross period, over the net (valid, specified conditional cash flow.

  11. Chemistry of the 5g Elements: Relativistic Calculations on Hexafluorides.

    Science.gov (United States)

    Dognon, Jean-Pierre; Pyykkö, Pekka

    2017-08-14

    A Periodic System was proposed for the elements 1-172 by Pyykkö on the basis of atomic and ionic calculations. In it, the elements 121-138 were nominally assigned to a 5g row. We now perform molecular, relativistic four-component DFT calculations and find that the hexafluorides of the elements 125-129 indeed enjoy occupied 5g states. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Chemistry of the 5g elements. Relativistic calculations on hexafluorides

    International Nuclear Information System (INIS)

    Dognon, Jean-Pierre; Pyykkoe, Pekka

    2017-01-01

    A Periodic System was proposed for the elements 1-172 by Pyykkoe on the basis of atomic and ionic calculations. In it, the elements 121-138 were nominally assigned to a 5g row. We now perform molecular, relativistic four-component DFT calculations and find that the hexafluorides of the elements 125-129 indeed enjoy occupied 5g states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Chemistry of the 5g elements. Relativistic calculations on hexafluorides

    Energy Technology Data Exchange (ETDEWEB)

    Dognon, Jean-Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France); Pyykkoe, Pekka [Department of Chemistry, University of Helsinki (Finland)

    2017-08-14

    A Periodic System was proposed for the elements 1-172 by Pyykkoe on the basis of atomic and ionic calculations. In it, the elements 121-138 were nominally assigned to a 5g row. We now perform molecular, relativistic four-component DFT calculations and find that the hexafluorides of the elements 125-129 indeed enjoy occupied 5g states. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Optimization of auxiliary basis sets for the LEDO expansion and a projection technique for LEDO-DFT.

    Science.gov (United States)

    Götz, Andreas W; Kollmar, Christian; Hess, Bernd A

    2005-09-01

    We present a systematic procedure for the optimization of the expansion basis for the limited expansion of diatomic overlap density functional theory (LEDO-DFT) and report on optimized auxiliary orbitals for the Ahlrichs split valence plus polarization basis set (SVP) for the elements H, Li--F, and Na--Cl. A new method to deal with near-linear dependences in the LEDO expansion basis is introduced, which greatly reduces the computational effort of LEDO-DFT calculations. Numerical results for a test set of small molecules demonstrate the accuracy of electronic energies, structural parameters, dipole moments, and harmonic frequencies. For larger molecular systems the numerical errors introduced by the LEDO approximation can lead to an uncontrollable behavior of the self-consistent field (SCF) process. A projection technique suggested by Löwdin is presented in the framework of LEDO-DFT, which guarantees for SCF convergence. Numerical results on some critical test molecules suggest the general applicability of the auxiliary orbitals presented in combination with this projection technique. Timing results indicate that LEDO-DFT is competitive with conventional density fitting methods. (c) 2005 Wiley Periodicals, Inc.

  15. A general procedure to evaluate many-body spin operator amplitudes from periodic calculations: application to cuprates

    Energy Technology Data Exchange (ETDEWEB)

    Moreira, Iberio de P R [Departament de Quimica Fisica and Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona and Parc CientIfic de Barcelona, C/ MartI i Franques 1, E-08028 Barcelona (Spain); Calzado, Carmen J [Departamento de Quimica Fisica, Universidad de Sevilla, C/ Prof. GarcIa Gonzalez s/n, E-41012 Sevilla (Spain); Malrieu, Jean-Paul [IRSAMC, Laboratoire de Physique Quantique, Universite Paul Sabatier, 118 Route de Narbonne, F-31062 Toulouse-Cedex (France); Illas, Francesc [Departament de Quimica Fisica and Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona and Parc CientIfic de Barcelona, C/ MartI i Franques 1, E-08028 Barcelona (Spain)

    2007-10-15

    A general procedure is presented which permits the form of an extended spin Hamiltonian to be established for a given magnetic solid and the magnitude of its terms to be evaluated from spin polarized, Hartree-Fock or density functional calculations carried out for periodic models. The computational strategy makes use of a general mapping between the energy of pertinent broken-symmetry solutions and the diagonal terms of the spin Hamiltonian in a local representation. From this mapping it is possible to determine not only the amplitude of the well-known two-body magnetic coupling constants between near-neighbor sites, but also the amplitudes of four-body cyclic exchange terms. A scrutiny of the on-site spin densities provides additional information and control of the many broken-symmetry solutions which can be found. The procedure is applied to the La{sub 2}CuO{sub 4}, Sr{sub 2}CuO{sub 2}F{sub 2}, Sr{sub 2}CuO{sub 2}Cl{sub 2} and Ca{sub 2}CuO{sub 2}Cl{sub 2} square lattices and the SrCu{sub 2}O{sub 3} ladder compound. It is shown that a proper description of the magnetic structure of these compounds requires that two- and four-body terms are explicitly included in the spin Hamiltonian. The implications for the interpretation of recent experiments are discussed.

  16. 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.

  17. Elementary calculation of the shutdown delay of a pile; Calcul elementaire de la periode d'extinction d'une pile

    Energy Technology Data Exchange (ETDEWEB)

    Yvon, J

    1949-04-01

    This study analyzes theoretically the progress of the shutdown of a nuclear pile (reactor) when a cadmium rod is introduced instantaneously. For simplification reasons, the environment of the pile is considered as homogenous and only thermal neutrons are considered (delayed neutrons are neglected). Calculation is made first for a plane configuration (plane vessel, plane multiplier without reflector, and plane multiplier with reflector), and then for a cylindrical configuration (multiplier without reflector, multiplier with infinitely thick reflector, finite cylindrical piles without reflector and with reflector). The self-sustain conditions are calculated for each case and the multiplication length and the shutdown delay are deduced. (J.S.)

  18. 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.

  19. 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.

  20. Crystal structures, DFT calculations, and Hirshfeld surface analyses of two new copper(II) and nickel(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine

    Science.gov (United States)

    Seifikar Ghomi, Leila; Behzad, Mahdi; Tarahhomi, Atekeh; Arab, Ali

    2017-12-01

    Two new Ni(II) and Cu(II) complexes of a tetradentate Schiff base ligand (1 and 2, respectively), derived from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-6-methoxy benzaldehyde, were synthesized and characterized by IR, UV-Vis, 1H NMR spectroscopy, and X-Ray crystallography. The central metal ions in both complexes are coordinated via the N2O2 coordination sphere of the ligand with square-planar geometry. DFT results revealed that the Msbnd N and Msbnd O interactions (M = Ni, Cu) are weaker than the typical covalent single bond indicating that ionic and electrostatic interactions are dominated in Msbnd N and Msbnd O bonds. Hirshfeld surface (HS) analyses of the studied structures 1 and 2 have been performed. The study using 3D HSs and 2D fingerprint plots (FPs) highlighted the dominant contacts H⋯H, C⋯H/H⋯C and O⋯H/H⋯O in both structures, and H⋯Cl in 2. The molecular assemblies held by C⋯O/O⋯C (in 1) and C⋯C (in 1 and 2) type dipole-dipole interactions are also found in the crystal packing contributing towards stability. The significant contributions arising from the mentioned interactions in crystal packing are also revealed from the Hirshfeld surface FPs showing a major contribution to total HS area for the H⋯H contacts for both structures.

  1. Electronic and Optical Properties of CuO Based on DFT+U and GW Approximation

    International Nuclear Information System (INIS)

    Ahmad, F; Agusta, M K; Dipojono, H K

    2016-01-01

    We report ab initio calculations of electronic structure and optical properties of monoclinic CuO based on DFT+U and GW approximation. CuO is an antiferromagnetic material with strong electron correlations. Our calculation shows that DFT+U and GW approximation sufficiently reliable to investigate the material properties of CuO. The calculated band gap of DFT+U for reasonable value of U slightly underestimates. The use of GW approximation requires adjustment of U value to get realistic result. Hybridization Cu 3dxz, 3dyz with O 2p plays an important role in the formation of band gap. The calculated optical properties based on DFT+U and GW corrections by solving Bethe-Salpeter are in good agreement with the calculated electronic properties and the experimental result. (paper)

  2. Implementation of DFT application on ternary optical computer

    Science.gov (United States)

    Junjie, Peng; Youyi, Fu; Xiaofeng, Zhang; Shuai, Kong; Xinyu, Wei

    2018-03-01

    As its characteristics of huge number of data bits and low energy consumption, optical computing may be used in the applications such as DFT etc. which needs a lot of computation and can be implemented in parallel. According to this, DFT implementation methods in full parallel as well as in partial parallel are presented. Based on resources ternary optical computer (TOC), extensive experiments were carried out. Experimental results show that the proposed schemes are correct and feasible. They provide a foundation for further exploration of the applications on TOC that needs a large amount calculation and can be processed in parallel.

  3. FAST TRACK COMMUNICATION A DFT + DMFT approach for nanosystems

    Science.gov (United States)

    Turkowski, Volodymyr; Kabir, Alamgir; Nayyar, Neha; Rahman, Talat S.

    2010-11-01

    We propose a combined density-functional-theory-dynamical-mean-field-theory (DFT + DMFT) approach for reliable inclusion of electron-electron correlation effects in nanosystems. Compared with the widely used DFT + U approach, this method has several advantages, the most important of which is that it takes into account dynamical correlation effects. The formalism is illustrated through different calculations of the magnetic properties of a set of small iron clusters (number of atoms 2 <= N <= 5). It is shown that the inclusion of dynamical effects leads to a reduction in the cluster magnetization (as compared to results from DFT + U) and that, even for such small clusters, the magnetization values agree well with experimental estimations. These results justify confidence in the ability of the method to accurately describe the magnetic properties of clusters of interest to nanoscience.

  4. 34 CFR 611.42 - How does the Secretary calculate the period of the scholarship recipient's service obligation?

    Science.gov (United States)

    2010-07-01

    ... scholarship recipient must teach in a high-need school of a high-need LEA in order to fulfill his or her... and 611.47 on the period the recipient has taught in one of its high-need schools; and (ii) Adjusting the period in which the recipient has taught in a high-need school to reflect the individual's...

  5. Calculation of the neutron noise induced by periodic deformations of a large sodium-cooled fast reactor core

    International Nuclear Information System (INIS)

    Zylbersztejn, F.; Tran, H.N.; Pazsit, I.; Filliatre, P.; Jammes, C.

    2014-01-01

    The subject of this paper is the calculation of the neutron noise induced by small-amplitude stationary radial variations of the core size (core expansion/compaction, also called core flowering) of a large sodium-cooled fast reactor. The calculations were performed on a realistic model of the European Sodium Fast Reactor (ESFR) core with a thermal output of 3600 MW(thermal), using a multigroup neutron noise simulator. The multigroup cross sections and their fluctuations that represent the core geometry changes for the neutron noise calculations were generated by the code ERANOS. The space and energy dependences of the noise source represented by the core expansion/compaction and the induced neutron noise are calculated and discussed. (authors)

  6. Oxovanadium(IV), cerium(III), thorium(IV) and dioxouranium(VI) complexes of 1-ethyl-4-hydroxy-3-(nitroacetyl)quinolin-2(1H)-one: Synthesis, spectral, thermal, fluorescence, DFT calculations, antimicrobial and antitumor studies

    Science.gov (United States)

    El-Shafiy, H. F.; Shebl, Magdy

    2018-03-01

    A new series of mononuclear oxovanadium(IV), cerium(III), thorium(IV) and dioxouranium(VI) complexes of a quinolinone ligand; 1-ethyl-4-hydroxy-3-(nitroacetyl)quinolin-2(1H)-one (H2L) have been synthesized. The metal complexes were characterized by different techniques such as elemental and thermal analyses, IR, 1H NMR, electronic, ESR, mass spectra and powder XRD, TEM in addition to magnetic susceptibility and conductivity measurements. The quinolinone ligand acts as a dibasic bidentate ligand forming mononuclear complexes, which can be formulated as: [(L)VO(H2O)2]·0.5H2O, [(L)M(NO3)x(H2O)y]·nH2O; M = Ce or Th, x = 1 or 2, y = 3 or 4 and n = 2 or 7 and [(L)UO2(H2O)x(MeOH)y]·nH2O; x = 2 or 3, y = 0 or 1 and n = 0.5 or 2.5. The photoluminescent properties of the prepared complexes were studied. The ligand and its thorium(IV) complex are characterized by an intense green emission. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. The geometry of the ligand and its oxovanadium(IV) complex has been optimized using density functional theory (DFT). Total energy, energy of HOMO and LUMO, dipole moment and structure activity relationship were performed and confirmed practical antimicrobial and antitumor results. The antimicrobial activity of the ligand and its metal complexes was conducted against the microorganisms S. aureus, K. pnemonia, E. coli, P. vulgaris and C. albicans and the MIC values were determined. The antitumor activity of the ligand and its metal complexes was investigated against human Hepatocelluar carcinoma and human breast cancer cell lines.

  7. Methyl Iodide Oxidative Addition to Rhodium(I) Complexes: a DFT ...

    African Journals Online (AJOL)

    NJD

    to the understanding of the role of the steric and electronic prop- erties of the different .... The pure Density Functional Theory (DFT) calculations were carried out using .... Since quantum computational methods are applied for the first time to ...

  8. Adaptive DFT-Based Interferometer Fringe Tracking

    Science.gov (United States)

    Wilson, Edward; Pedretti, Ettore; Bregman, Jesse; Mah, Robert W.; Traub, Wesley A.

    2005-12-01

    An automatic interferometer fringe tracking system has been developed, implemented, and tested at the Infrared Optical Telescope Array (IOTA) Observatory at Mount Hopkins, Arizona. The system can minimize the optical path differences (OPDs) for all three baselines of the Michelson stellar interferometer at IOTA. Based on sliding window discrete Fourier-transform (DFT) calculations that were optimized for computational efficiency and robustness to atmospheric disturbances, the algorithm has also been tested extensively on offline data. Implemented in ANSI C on the 266 MHz PowerPC processor running the VxWorks real-time operating system, the algorithm runs in approximately [InlineEquation not available: see fulltext.] milliseconds per scan (including all three interferograms), using the science camera and piezo scanners to measure and correct the OPDs. The adaptive DFT-based tracking algorithm should be applicable to other systems where there is a need to detect or track a signal with an approximately constant-frequency carrier pulse. One example of such an application might be to the field of thin-film measurement by ellipsometry, using a broadband light source and a Fourier-transform spectrometer to detect the resulting fringe patterns.

  9. Adaptive DFT-Based Interferometer Fringe Tracking

    Directory of Open Access Journals (Sweden)

    Wesley A. Traub

    2005-09-01

    Full Text Available An automatic interferometer fringe tracking system has been developed, implemented, and tested at the Infrared Optical Telescope Array (IOTA Observatory at Mount Hopkins, Arizona. The system can minimize the optical path differences (OPDs for all three baselines of the Michelson stellar interferometer at IOTA. Based on sliding window discrete Fourier-transform (DFT calculations that were optimized for computational efficiency and robustness to atmospheric disturbances, the algorithm has also been tested extensively on offline data. Implemented in ANSI C on the 266 MHz PowerPC processor running the VxWorks real-time operating system, the algorithm runs in approximately 2.0 milliseconds per scan (including all three interferograms, using the science camera and piezo scanners to measure and correct the OPDs. The adaptive DFT-based tracking algorithm should be applicable to other systems where there is a need to detect or track a signal with an approximately constant-frequency carrier pulse. One example of such an application might be to the field of thin-film measurement by ellipsometry, using a broadband light source and a Fourier-transform spectrometer to detect the resulting fringe patterns.

  10. Contribution to harmonic balance calculations of self-sustained periodic oscillations with focus on single-reed instruments.

    Science.gov (United States)

    Farner, Snorre; Vergez, Christophe; Kergomard, Jean; Lizée, Aude

    2006-03-01

    The harmonic balance method (HBM) was originally developed for finding periodic solutions of electronical and mechanical systems under a periodic force, but has been adapted to self-sustained musical instruments. Unlike time-domain methods, this frequency-domain method does not capture transients and so is not adapted for sound synthesis. However, its independence of time makes it very useful for studying any periodic solution, whether stable or unstable, without care of particular initial conditions in time. A computer program for solving general problems involving nonlinearly coupled exciter and resonator, HARMBAL, has been developed based on the HBM. The method as well as convergence improvements and continuation facilities are thoroughly presented and discussed in the present paper. Applications of the method are demonstrated, especially on problems with severe difficulties of convergence: the Helmholtz motion (square signals) of single-reed instruments when no losses are taken into account, the reed being modeled as a simple spring.

  11. Comparison of experimental and DFT-calculated NMR chemical shifts of 2-amino and 2-hydroxyl substituted phenyl benzimidazoles, benzoxazoles and benzothiazoles in four solvents using the IEF-PCM solvation model.

    Science.gov (United States)

    Pierens, Gregory K; Venkatachalam, T K; Reutens, David C

    2016-04-01

    A comparative study of experimental and calculated NMR chemical shifts of six compounds comprising 2-amino and 2-hydroxy phenyl benzoxazoles/benzothiazoles/benzimidazoles in four solvents is reported. The benzimidazoles showed interesting spectral characteristics, which are discussed. The proton and carbon chemical shifts were similar for all solvents. The largest chemical shift deviations were observed in benzene. The chemical shifts were calculated with density functional theory using a suite of four functionals and basis set combinations. The calculated chemical shifts revealed a good match to the experimentally observed values in most of the solvents. The mean absolute error was used as the primary metric. The use of an additional metric is suggested, which is based on the order of chemical shifts. The DP4 probability measures were also used to compare the experimental and calculated chemical shifts for each compound in the four solvents. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  12. Entropy method of measuring and evaluating periodicity of quasi-periodic trajectories

    Science.gov (United States)

    Ni, Yanshuo; Turitsyn, Konstantin; Baoyin, Hexi; Junfeng, Li

    2018-06-01

    This paper presents a method for measuring the periodicity of quasi-periodic trajectories by applying discrete Fourier transform (DFT) to the trajectories and analyzing the frequency domain within the concept of entropy. Having introduced the concept of entropy, analytical derivation and numerical results indicate that entropies increase as a logarithmic function of time. Periodic trajectories typically have higher entropies, and trajectories with higher entropies mean the periodicities of the motions are stronger. Theoretical differences between two trajectories expressed as summations of trigonometric functions are also derived analytically. Trajectories in the Henon-Heiles system and the circular restricted three-body problem (CRTBP) are analyzed with the indicator entropy and compared with orthogonal fast Lyapunov indicator (OFLI). The results show that entropy is a better tool for discriminating periodicity in quasiperiodic trajectories than OFLI and can detect periodicity while excluding the spirals that are judged as periodic cases by OFLI. Finally, trajectories in the vicinity of 243 Ida and 6489 Golevka are considered as examples, and the numerical results verify these conclusions. Some trajectories near asteroids look irregular, but their higher entropy values as analyzed by this method serve as evidence of frequency regularity in three directions. Moreover, these results indicate that applying DFT to the trajectories in the vicinity of irregular small bodies and calculating their entropy in the frequency domain provides a useful quantitative analysis method for evaluating orderliness in the periodicity of quasi-periodic trajectories within a given time interval.

  13. Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: the case of LiH.

    Science.gov (United States)

    Usvyat, Denis; Civalleri, Bartolomeo; Maschio, Lorenzo; Dovesi, Roberto; Pisani, Cesare; Schütz, Martin

    2011-06-07

    The atomic orbital basis set limit is approached in periodic correlated calculations for solid LiH. The valence correlation energy is evaluated at the level of the local periodic second order Møller-Plesset perturbation theory (MP2), using basis sets of progressively increasing size, and also employing "bond"-centered basis functions in addition to the standard atom-centered ones. Extended basis sets, which contain linear dependencies, are processed only at the MP2 stage via a dual basis set scheme. The local approximation (domain) error has been consistently eliminated by expanding the orbital excitation domains. As a final result, it is demonstrated that the complete basis set limit can be reached for both HF and local MP2 periodic calculations, and a general scheme is outlined for the definition of high-quality atomic-orbital basis sets for solids. © 2011 American Institute of Physics

  14. 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.

  15. Molecular design of high performance fused heteroacene radical cations: A DFT study

    International Nuclear Information System (INIS)

    Kawabata, Hiroshi; Ohmori, Shigekazu; Matsushige, Kazumi; Tachikawa, Hiroto

    2008-01-01

    Hybrid density functional theory (DFT) calculations have been carried out for neutral and radical cation of fused furan oligomer, denoted by F(n) where n means number of furan rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused furan was also investigated using one-dimensional periodic boundary condition (PBC) for comparison. It was found that the reorganization energy of radical cation of F(n) from vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that F(n) has an effective hole transport property. It was found that the cation radical of F(n) has a low energy band at near IR region, which is strongly correlated to hole conductivity. The relation between the electronic states and hole conductivity was discussed on the basis of theoretical calculations

  16. Adsorption of beryllium atoms and clusters both on graphene and in a bilayer of graphite investigated by DFT.

    Science.gov (United States)

    Ferro, Yves; Fernandez, Nicolas; Allouche, Alain; Linsmeier, Christian

    2013-01-09

    We herein investigate the interaction of beryllium with a graphene sheet and in a bilayer of graphite by means of periodic DFT calculations. In all cases, we find the beryllium atoms to be more weakly bonded on graphene than in the bilayer. Be(2) forms both magnetic and non-magnetic structures on graphene depending on the geometrical configuration of adsorption. We find that the stability of the Be/bilayer system increases with the size of the beryllium clusters inserted into the bilayer of graphite. We also find a charge transfer from beryllium to the graphite layers. All these results are analysed in terms of electronic structure.

  17. Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE and TCNQ, from DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Sarkar, B.; Duboc, C.; Kaim, A.

    2009-01-01

    Roč. 140, č. 7 (2009), s. 765-773 ISSN 0026-9247 R&D Projects: GA MŠk OC 139; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : Density functional calculations * Transition metal compounds * Ruthenium complexes * redox states Subject RIV: CG - Electrochemistry Impact factor: 1.312, year: 2009

  18. Studies of the electron density in the highest occupied molecular orbitals of PH 3, PF 3 and P(CH 3) 3 by electron momentum spectroscopy and Hartree-Fock, MRSD-CI and DFT calculations

    Science.gov (United States)

    Rolke, J.; Brion, C. E.

    1996-06-01

    The spherically averaged momentum profiles for the highest occupied molecular orbitals of PF 3 and P(CH 3) 3 have been obtained by electron momentum spectroscopy. The measurements provide a stringent test of basis set effects and the quality of ab-initio methods in the description of these larger molecular systems. As in previous work on the methyl-substituted amines, intuitive arguments fail to predict the correct amount of s- and p-type contributions to the momentum profile while delocalized molecular orbital concepts provide a more adequate description of the HOMOs. The experimental momentum profiles have been compared with theoretical momentum profiles calculated at the level of the target Hartree-Fock approximation with a range of basis sets. New Hartree-Fock calculations are also presented for the HOMO of PH 3 and compared to previously published experimental and theoretical momentum profiles. The experimental momentum profiles have further been compared to calculations at the level of the target Kohn-Sham approximation using density functional theory with the local density approximation and also with gradient corrected (non-local) exchange correlation potentials. In addition, total energies and dipole moments have been calculated for all three molecules by the various theoretical methods and compared to experimental values. Calculated 'density difference maps' show the regions where the HOMO momentum and position electron densities of PF 3 and P(CH 3) 3 change relative to the corresponding HOMO density of PH 3. The results suggest that methyl groups have an electron-attracting effect (relative to H) on the HOMO charge density in trimethyl phosphines. These conclusions are supported by a consideration of dipole moments and the 31P NMR chemical shifts for PH 3, PF 3 and P(CH 3) 3.

  19. On the full exploitation of symmetry in periodic (as well as molecular) self-consistent-field ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Orlando, Roberto, E-mail: roberto.orlando@unito.it; Erba, Alessandro; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); De La Pierre, Marco [Dipartimento di Chimica, Università di Torino and NIS, Nanostructured Interfaces and Surfaces, Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia); Zicovich-Wilson, Claudio M. [Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Av. Universidad, 1001, Col. Chamilpa, 62209 Cuernavaca (Morelos) (Mexico)

    2014-09-14

    Use of symmetry can dramatically reduce the computational cost (running time and memory allocation) of self-consistent-field ab initio calculations for molecular and crystalline systems. Crucial for running time is symmetry exploitation in the evaluation of one- and two-electron integrals, diagonalization of the Fock matrix at selected points in reciprocal space, reconstruction of the density matrix. As regards memory allocation, full square matrices (overlap, Fock, and density) in the Atomic Orbital (AO) basis are avoided and a direct transformation from the packed AO to the symmetry adapted crystalline orbital basis is performed, so that the largest matrix to be handled has the size of the largest sub-block in the latter basis. Quantitative examples, referring to the implementation in the CRYSTAL code, are given for high symmetry families of compounds such as carbon fullerenes and nanotubes.

  20. A Conceptual Model for Calculating the Return of Costs Invested in the Creation of an Economic Security Service, During a Short-Term Period

    Directory of Open Access Journals (Sweden)

    Melikhova Tetiana O.

    2018-02-01

    Full Text Available The article is aimed at suggesting methods for calculating the short-term period of return of costs invested in creation of an economic security service. The article considers approaches to calculation of the period of return of costs, advanced at the level of enterprise, which build the methodical basis for definition of such period. At the level of structural subdivisions of enterprise, which do not produce products, it is suggested to use conditional money flow as a source of financing advanced costs. The calculation of the short-term return on investment at the enterprise level provides for: allocation of expenses for the permanent and the replacement parts during the year; determination of the production of money flow and the money flow accumulated during the year. Annual depreciation payments are the basis of fixed costs. Methods of determination of the gross, net, valid, and specified periods of return of costs, advanced during the year for introduction of an economic security service at enterprise, have been suggested.

  1. Calculation of spin-spin zero-field splitting within periodic boundary conditions: Towards all-electron accuracy

    Science.gov (United States)

    Biktagirov, Timur; Schmidt, Wolf Gero; Gerstmann, Uwe

    2018-03-01

    For high-spin centers, one of the key spectroscopic fingerprints is the zero-field splitting (ZFS) addressable by electron paramagnetic resonance. In this paper, an implementation of the spin-spin contribution to the ZFS tensor within the projector augmented-wave (PAW) formalism is reported. We use a single-determinant approach proposed by M. J. Rayson and P. R. Briddon [Phys. Rev. B 77, 035119 (2008), 10.1103/PhysRevB.77.035119], and complete it by adding a PAW reconstruction term which has not been taken into account before. We benchmark the PAW approach against a well-established all-electron method for a series of diatomic radicals and defects in diamond and cubic silicon carbide. While for some of the defect centers the PAW reconstruction is found to be almost negligible, in agreement with the common assumption, we show that in general it significantly improves the calculated ZFS towards the all-electron results.

  2. 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.

  3. Molecular Structure and Chemical Shift Assignments of 4-(2-Methoxy-4-Methylphenoxy)Phthalonitrile (C16H12N2O2) By DFT And AB Initio HF Calculations

    International Nuclear Information System (INIS)

    Tarcan, E.

    2008-01-01

    The molecular geometry, gauge including atomic orbital (GIAO) 1 H and 13 C chemical shift values of 4-(2-Methoxy-4-methylphenoxy)phthalonitrile (C 1 6H 1 2N 2 O 2 ) in the ground state have been calculated by using the Hartree-Fock (HF) and density functional methods (B3LYP and BLYP) with 6-31G(d) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The optimized bond length numbers with bond angels are in good agreement with the X-ray data

  4. Depletion study, withdrawal period calculation and bioaccumulation of sulfamethazine in tilapia (Oreochromis niloticus) treated with medicated feed.

    Science.gov (United States)

    Nunes, Kátia S D; Vallim, José H; Assalin, Márcia R; Queiroz, Sonia C N; Paraíba, Lourival C; Jonsson, Claudio M; Reyes, Felix G R

    2018-04-01

    The residue depletion of sulfamethazine (SMZ) was evaluated in tilapia (Oreochromis niloticus) after 11 days of administration of medicated feed containing SMZ, at the dose of 422 mg/kg body weight (bw). The determination of SMZ in feed and tilapia fillet was carried out using the QuEChERS approach for sample preparation, and high performance liquid chromatography with diode array detector (HPLC-DAD) and ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QToF-MS) for quantitation, respectively. Both methods were validated based on international and Brazilian guidelines and shown to be suitable for the intended purposes. The withdrawal period to reach the maximum residue level (MRL) of 100 μg/kg, according to the European Union (EU) legislative framework to all substances belonging to the sulfonamide (SA) group (EU, 2010), was 10 days (260 °C-day). After treatment, the maximum level of SMZ accumulation in the tilapia muscle was 1.6 mg/kg. SMZ was shown to be quickly excreted by tilapia. Thus, considering the acceptable daily intake of SMZ established by the Codex Commission (0-0.05 mg/kg bw), and a factor of 5 times the upper amount of fish consumption in Brazil (38 kg/year), this study showed that there is a low risk of adverse effects to consumers. This study offers subsidies not only for the establishment of public policies with regard to the use of veterinary drugs currently not allowed in a country by their legal legislative framework for fish farming, but also to fish producers for the proper handling to ensure safe fish fillets. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. 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.

  6. Copper(II) and zinc(II) as metal-carboxylate coordination complexes based on (1-methyl-1H-benzo[d]imidazol-2-yl) methanol derivative: Synthesis, crystal structure, spectroscopy, DFT calculations and antioxidant activity

    Science.gov (United States)

    Benhassine, Anfel; Boulebd, Houssem; Anak, Barkahem; Bouraiou, Abdelmalek; Bouacida, Sofiane; Bencharif, Mustapha; Belfaitah, Ali

    2018-05-01

    This work presents a combined experimental and theoretical study of two new metal-carboxylate coordination compounds. These complexes were prepared from (1-methyl-1H-benzimidazol-2-yl)methanol under mild conditions. The structures of the prepared compounds were characterized by single-crystal X-ray analysis, FTIR and UV-Vis spectroscopy. In the Cupper complex, the Cu(II) ion is coordinated by two ligands, which act as bidentate chelator through the non-substituted N and O atoms, and two carboxylicg oxygen atoms, displaying a hexa-coordinated compound in a distorted octahedral geometry, while in the Zinc complex the ligand is ligated to the Zn(II) ion in monodentate fashion through the N atom, and the metal ion is also bonded to carboxylic oxygen atoms. The tetra-coordinated compound displays a distorted tetrahedral shape. The density functional theory calculations are carried out for the determination of the optimized structures. The electronic transitions and fundamental vibrational wave numbers are calculated and are in good agreement with experimental. In addition, the ligand and its Cu(II) and Zn(II) complexes were screened and evaluated for their potential as DPPH radical scavenger.

  7. Consistent gaussian basis sets of double- and triple-zeta valence with polarization quality of the fifth period for solid-state calculations.

    Science.gov (United States)

    Laun, Joachim; Vilela Oliveira, Daniel; Bredow, Thomas

    2018-02-22

    Consistent basis sets of double- and triple-zeta valence with polarization quality for the fifth period have been derived for periodic quantum-chemical solid-state calculations with the crystalline-orbital program CRYSTAL. They are an extension of the pob-TZVP basis sets, and are based on the full-relativistic effective core potentials (ECPs) of the Stuttgart/Cologne group and on the def2-SVP and def2-TZVP valence basis of the Ahlrichs group. We optimized orbital exponents and contraction coefficients to supply robust and stable self-consistent field (SCF) convergence for a wide range of different compounds. The computed crystal structures are compared to those obtained with standard basis sets available from the CRYSTAL basis set database. For the applied hybrid density functional PW1PW, the average deviations of calculated lattice constants from experimental references are smaller with pob-DZVP and pob-TZVP than with standard basis sets. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  8. Crystal structures and DFT calculations of mixed chloride-azide zinc(II) and chloride-isocyanate cadmium(II) complexes with the condensation product of 2-quinolinecarboxaldehyde and Girard's T reagent

    Science.gov (United States)

    Anđelković, Katarina; Pevec, Andrej; Grubišić, Sonja; Turel, Iztok; Čobeljić, Božidar; Milenković, Milica R.; Keškić, Tanja; Radanović, Dušanka

    2018-06-01

    The mixed chloride-azide [ZnL(N3)1.65Cl0.35] (1) and chloride-isocyanate [CdL(NCO)1.64Cl0.36] (2) complexes with the condensation product of 2-quinolinecarboxaldehyde and trimethylammonium acetohydrazide chloride (Girard's T reagent) (HLCl) have been prepared and characterized by X-ray crystallography. In complexes 1 and 2, Zn1 and Cd1 ions, respectively, are five-coordinated in a distorted square based pyramidal geometry with NNO set of donor atoms of deprotonated hydrazone ligand and two monodentate ligands N3- and/or N3- and Cl- in the case of 1 and OCN- and/or OCN- and Cl- in the case of 2. The structural parameters of 1 and 2 have been discussed in relation to those of previously reported M(II) complexes with the same hydrazone ligand. Density functional theory calculations have been employed to study the interaction between the Zn2+ and Cd2+ ions and ligands. High affinity of ligands towards the Zn2+ and Cd2+ ions are predicted for both complexes.

  9. The Improvement of the Methodological Approaches to Calculating the Payback Period for Investment in order to Estimate Expenses on Establishing the Economic Security Service of an Enterprise

    Directory of Open Access Journals (Sweden)

    Melikhova Tetiana O.

    2018-03-01

    Full Text Available The aim of the article is to improve the methodological approaches to calculating the payback period for investment in order to determine the payback period for expenses on establishing the economic security service of an enterprise. It is found that the source of payback of investment at the enterprise level is cash flow product. These revenues (the result go to formation of a cash flow (expenses used to finance investment and financial activities. There proposed methods for determining the gross, net, actual, and specified payback periods for advanced investments in the long-term, which use the accumulated product of cash flow or accumulated cash flow as a source of financing. Analytic relationships between the gross, net, current, and specified payback periods for advanced investments that take into account the relationship between the accumulated gross, net, current and specified cash flows are proposed. The considered options for payback of advanced investment at the enterprise level will provide an opportunity to develop methods for determining the payback period for expenses on establishing the economic security service of an enterprise.

  10. 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.

  11. 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.

  12. DFT Study of dimers of dimethyl sulfoxide in gas phase

    Directory of Open Access Journals (Sweden)

    Reza Fazaeli

    2014-10-01

    Full Text Available Density functional (DFT calculations at M05-2x/aug-cc-pVDZ level were used to analyze the interactions between dimethyl sulfoxide (DMSO dimers. The structures obtained have been ana-lyzed with the Atoms in Molecules (AIMs and Natural Bond Orbital (NBO methodologies. Four minima were located on the potential energy surface of the dimers. Three types of interac-tions are observed, CH•••O, CH•••S hydrogen bonds and orthogonal interaction between the lone pair of the oxygen with the electron-deficient region of the sulfur atom. Stabilization energies of dimers including BSSE and ZPE are in the range 27–40 kJmol-1. The most stable conformers of dimers at DFT level is cyclic structure with antiparallel orientation of S=O groups pairing with three C–H∙∙∙O and a S∙∙∙O interactions.

  13. 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.

  14. 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...

  15. Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory.

    Science.gov (United States)

    Hine, Nicholas D M; Dziedzic, Jacek; Haynes, Peter D; Skylaris, Chris-Kriton

    2011-11-28

    We present a comparison of methods for treating the electrostatic interactions of finite, isolated systems within periodic boundary conditions (PBCs), within density functional theory (DFT), with particular emphasis on linear-scaling (LS) DFT. Often, PBCs are not physically realistic but are an unavoidable consequence of the choice of basis set and the efficacy of using Fourier transforms to compute the Hartree potential. In such cases the effects of PBCs on the calculations need to be avoided, so that the results obtained represent the open rather than the periodic boundary. The very large systems encountered in LS-DFT make the demands of the supercell approximation for isolated systems more difficult to manage, and we show cases where the open boundary (infinite cell) result cannot be obtained from extrapolation of calculations from periodic cells of increasing size. We discuss, implement, and test three very different approaches for overcoming or circumventing the effects of PBCs: truncation of the Coulomb interaction combined with padding of the simulation cell, approaches based on the minimum image convention, and the explicit use of open boundary conditions (OBCs). We have implemented these approaches in the ONETEP LS-DFT program and applied them to a range of systems, including a polar nanorod and a protein. We compare their accuracy, complexity, and rate of convergence with simulation cell size. We demonstrate that corrective approaches within PBCs can achieve the OBC result more efficiently and accurately than pure OBC approaches.

  16. The pink pigment prodigiosin: Vibrational spectroscopy and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Jehlička, J.; Němec, I.; Varnali, T.; Culka, A.; Svatoš, A.; Frank, Otakar; Oren, A.; Edwards, G.M.

    2016-01-01

    Roč. 134, NOV 2016 (2016), s. 234-243 ISSN 0143-7208 Institutional support: RVO:61388955 Keywords : prodigiosin * serratia marcescens * raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 3.473, year: 2016

  17. 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

  18. Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

    Science.gov (United States)

    Wu, Dandan; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

    2017-07-01

    The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

  19. Hydrogen molecule on lithium adsorbed graphene: A DFT study

    International Nuclear Information System (INIS)

    Kaur, Gagandeep; Gupta, Shuchi; Gaganpreet; Dharamvir, Keya

    2016-01-01

    Electronic structure calculations for the adsorption of molecular hydrogen on lithium (Li) decorated and pristine graphene have been studied systematically using SIESTA code [1] within the framework of the first-principle DFT under the Perdew-Burke-Ernzerhof (PBE) form of the generalized gradient approximation (GGA)[2], including spin polarization. The energy of adsorption of hydrogen molecule on graphene is always enhanced by the presence of co-adsorbed lithium. The most efficient adsorption configuration is when H 2 is lying parallel to lithium adsorbed graphene which is in contrast to its adsorption on pristine graphene (PG) where it prefers perpendicular orientation.

  20. Methanol to olefin Conversion on HSAPO-34 zeolite from periodic density functional theory calculations: a complete cycle of side chain hydrocarbon pool mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.M.; Wang, Y.D.; Xie, Z.K.; Liu, Z.P. [SINOPEC, Shanghai (China)

    2009-03-15

    For its unique position in the coal chemical industry, the methanol to olefin (MTO) reaction has been a hot topic in zeolite catalysis. Due to the complexities of catalyst structure and reaction networks, many questions such as how the olefin chain is built from methanol remain elusive. On the basis of periodic density functional theory calculations, this work establishes the first complete catalytic cycle for MTO reaction via hexamethylbenzene (HMB) trapped in HSAPO-34 zeolite based on the so-called side chain hydrocarbon pool mechanism. The cycle starts from the methylation of HMB that leads to heptamethylbenzenium ion (heptaMB{sup +}) intermediate. This is then followed by the growth of side chain via repeated deprotonation of benzenium ions and methylation of the exocyclic double bond. Ethene and propene can finally be released from the side ethyl and isopropyl groups of benzenium ions by deprotonation and subsequent protonation steps. We demonstrate that (i) HMB/HSAPO-34 only yields propene as the primary product based on the side chain hydrocarbon pool mechanism and (ii) an indirect proton-shift step mediated by water that is always available in the system is energetically more favorable than the traditionally regarded internal hydrogen-shift step. Finally, the implications of our results toward understanding the effect of acidity of zeolite on MTO activity are also discussed.

  1. Issues in first-principles calculations for defects in semiconductors and oxides

    International Nuclear Information System (INIS)

    Nieminen, Risto M

    2009-01-01

    Recent advances in density-functional theory (DFT) calculations of defect electronic properties in semiconductors and insulators are discussed. In particular, two issues are addressed: the band-gap underestimation of standard density-functional methods with its harmful consequences for the positioning of defect-related levels in the band-gap region, and the slow convergence of calculated defect properties when the periodic supercell approach is used. Systematic remedies for both of these deficiencies are now available, and are being implemented in the context of popular DFT codes. This should help in improving the parameter-free accuracy and thus the predictive power of the methods to enable unambiguous explanation of defect-related experimental observations. These include not only the various fingerprint spectroscopies for defects but also their thermochemistry and dynamics, i.e. the temperature-dependent concentration and diffusivities of defects under various doping conditions and in different stoichiometries

  2. 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...

  3. Experimental and DFT study of thiol-stabilized Pt/CNTs catalysts.

    Science.gov (United States)

    Li, L; Chen, S G; Wei, Z D; Qi, X Q; Xia, M R; Wang, Y Q

    2012-12-28

    Using a combination of experiments and density functional theory (DFT) calculations, we explored the mechanisms of the stabilization effect of the thiolized (-SH) group on the Pt/SH-CNTs catalyst. Pt particles supported on the hydroxyl functionalized CNTs (Pt/OH-CNTs) are synthesized as a baseline for comparison. Experimentally, the platinum on OH-CNTs has a stronger tendency for aggregation than that on SH-CNTs. The differences in the oxidation resistance, migration activation energy, and corrosion resistance between the Pt/SH-CNTs and Pt/OH-CNTs are calculated using DFT. The DFT calculations indicate that the -SH group enhances the oxidation resistance of the Pt cluster and CNTs and restricts Pt migration on the CNTs. DFT calculations also suggest that the enhanced stability of Pt/SH-CNTs originates from the increased interaction between Pt and SH-CNTs and the depressed d-band center of the Pt NPs. Thus, the functional groups on the CNTs used for stabilization of supported Pt NPs should provide a deposit and anchor site for Pt NPs and maintain the perfect structure of CNTs rather than destroying it.

  4. Synthesis, spectroscopy, X-ray crystallography, and DFT computations of nanosized phosphazenes

    Czech Academy of Sciences Publication Activity Database

    Shariatinia, Z.; Moghadam, E.J.; Maghsoudi, N.; Mousavi, H.S.M.; Dušek, Michal; Eigner, Václav

    2015-01-01

    Roč. 641, č. 5 (2015), s. 967-978 ISSN 0044-2313 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : phosphazene * ultrasonic * nanoparticle * x-ray crystallography * DFT calculation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.261, year: 2015

  5. Complexation of the cesium cation with lithium ionophore VIII: extraction and DFT study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Novák, Vít; Vaňura, P.; Bouř, Petr

    2013-01-01

    Roč. 298, č. 3 (2013), s. 2065-2068 ISSN 0236-5731 Institutional support: RVO:61388963 Keywords : cesium cation * lithium ionophore VIII * complexation * extraction and stability constants * water-nitrobenzene system * DFT calculations * structures Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 1.415, year: 2013

  6. A rational synthesis of a novel imidazo[4,5-f][1,10]phenanthroline templated Schiff base: Characterization, photoluminescence and DFT/TD-DFT study

    Directory of Open Access Journals (Sweden)

    S. Karslıoğlu

    2017-07-01

    Full Text Available A new imidazo[4,5-f][1,10]phenanthroline (imp derivative imidazo-N5,N6-bis((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-ylphenylmethylene-1,10-phenanthroline-5,6-diamine (impap was synthesized in five steps starting from bare phenanthroline (phen precursors. The novel compound was fully characterized by 1H-NMR, IR, elemental analysis and electrospray ionization mass spectroscopy (ESI-MS techniques. Solid state emission spectrum of impap showed two distinct strong emission maxima with large Stokes shifts. The ground state gas phase geometry of impap was predicted by DFT calculations. Excited state properties of the molecule were examined through TD-DFT calculations conducted at the optimized geometry. Responsible transitions for the strong fluorescence of impap were assigned to single component charge transfer transitions with large oscillator strengths based on the ground state calculated molecular orbital contributions.

  7. 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.

  8. Reactive sites influence in PMMA oligomers reactivity: a DFT study

    Science.gov (United States)

    Paz, C. V.; Vásquez, S. R.; Flores, N.; García, L.; Rico, J. L.

    2018-01-01

    In this work, we present a theoretical study of methyl methacrylate (MMA) living anionic polymerization. The study was addressed to understanding two important experimental observations made for Michael Szwarc in 1956. The unexpected effect of reactive sites concentration in the propagation rate, and the self-killer behavior of MMA (deactivating of living anionic polymerization). The theoretical calculations were performed by density functional theory (DFT) to obtain the frontier molecular orbitals values. These values were used to calculate and analyze the chemical interaction descriptors in DFT-Koopmans’ theorem. As a result, it was observed that the longest chain-length species (related with low concentration of reactive sites) exhibit the highest reactivity (behavior associated with the increase of the propagation rate). The improvement in this reactivity was attributed to the crosslinking produced in the polymethyl methacrylate chains. Meanwhile, the self-killer behavior was associated with the intermolecular forces present in the reactive sites. This behavior was associated to an obstruction in solvation, since the active sites remained active through all propagation species. The theoretical results were in good agreement with the Szwarc experiments.

  9. 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.

  10. Implementation of Constrained DFT for Computing Charge Transfer Rates within the Projector Augmented Wave Method

    DEFF Research Database (Denmark)

    Melander, Marko; Jónsson, Elvar Örn; Mortensen, Jens Jørgen

    2016-01-01

    molecules to periodic systems in one-, two-, or three-dimensions. As such, this implementation is relevant for a wide variety of applications. We also present how to extract the electronic coupling element and reorganization energy from the resulting diabatic cDFT-PAW wave functions for the parametrization...

  11. A DFT study on benzene adsorption over tungsten sulfides: surface model and adsorption geometries

    NARCIS (Netherlands)

    Koide, R.; Hensen, E.J.M.; Paul, J.F.; Cristol, S.; Payen, E.; Nakamura, H.; Santen, van R.A.

    2007-01-01

    Benzene adsorption on a WS2(100) surface was studied by ab initio periodic DFT computations. Benzene adsorption is facile on the bridge site of the bare W edge via ¿2 or ¿3 coordination. Taking into account the stable configuration at the W edge under typical hydrotreating reaction conditions (623

  12. Thz Spectroscopy and DFT Modeling of Intermolecular Vibrations in Hydrophobic Amino Acids

    Science.gov (United States)

    Williams, michael R. C.; Aschaffenburg, Daniel J.; Schmuttenmaer, Charles A.

    2013-06-01

    Vibrations that involve intermolecular displacements occur in molecular crystals at frequencies in the 0.5-5 THz range (˜15-165 cm^{-1}), and these motions are direct indicators of the interaction potential between the molecules. The intermolecular potential energy surface of crystalline hydrophobic amino acids is inherently interesting simply because of the wide variety of forces (electrostatic, dipole-dipole, hydrogen-bonding, van der Waals) that are present. Furthermore, an understanding of these particular interactions is immediately relevant to important topics like protein conformation and pharmaceutical polymorphism. We measured the low-frequency absorption spectra of several polycrystalline hydrophobic amino acids using THz time-domain spectroscopy, and in addition we carried out DFT calculations using periodic boundary conditions and an exchange-correlation functional that accounts for van der Waals dispersion forces. We chose to investigate a series of similar amino acids with closely analogous unit cells (leucine, isoleucine, and allo-isoleucine, in racemic or pseudo-racemic mixtures). This allows us to consider trends in the vibrational spectra as a function of small changes in molecular arrangement and/or crystal geometry. In this way, we gain confidence that peak assignments are not based on serendipitous similarities between calculated and observed features.

  13. GW quasiparticle bandgaps of anatase TiO2 starting from DFT + U.

    Science.gov (United States)

    Patrick, Christopher E; Giustino, Feliciano

    2012-05-23

    We investigate the quasiparticle band structure of anatase TiO(2), a wide gap semiconductor widely employed in photovoltaics and photocatalysis. We obtain GW quasiparticle energies starting from density-functional theory (DFT) calculations including Hubbard U corrections. Using a simple iterative procedure we determine the value of the Hubbard parameter yielding a vanishing quasiparticle correction to the fundamental bandgap of anatase TiO(2). The bandgap (3.3 eV) calculated using this optimal Hubbard parameter is smaller than the value obtained by applying many-body perturbation theory to standard DFT eigenstates and eigenvalues (3.7 eV). We extend our analysis to the rutile polymorph of TiO(2) and reach similar conclusions. Our work highlights the role of the starting non-interacting Hamiltonian in the calculation of GW quasiparticle energies in TiO(2) and suggests an optimal Hubbard parameter for future calculations.

  14. Analyzing the errors of DFT approximations for compressed water systems

    International Nuclear Information System (INIS)

    Alfè, D.; Bartók, A. P.; Csányi, G.; Gillan, M. J.

    2014-01-01

    We report an extensive study of the errors of density functional theory (DFT) approximations for compressed water systems. The approximations studied are based on the widely used PBE and BLYP exchange-correlation functionals, and we characterize their errors before and after correction for 1- and 2-body errors, the corrections being performed using the methods of Gaussian approximation potentials. The errors of the uncorrected and corrected approximations are investigated for two related types of water system: first, the compressed liquid at temperature 420 K and density 1.245 g/cm 3 where the experimental pressure is 15 kilobars; second, thermal samples of compressed water clusters from the trimer to the 27-mer. For the liquid, we report four first-principles molecular dynamics simulations, two generated with the uncorrected PBE and BLYP approximations and a further two with their 1- and 2-body corrected counterparts. The errors of the simulations are characterized by comparing with experimental data for the pressure, with neutron-diffraction data for the three radial distribution functions, and with quantum Monte Carlo (QMC) benchmarks for the energies of sets of configurations of the liquid in periodic boundary conditions. The DFT errors of the configuration samples of compressed water clusters are computed using QMC benchmarks. We find that the 2-body and beyond-2-body errors in the liquid are closely related to similar errors exhibited by the clusters. For both the liquid and the clusters, beyond-2-body errors of DFT make a substantial contribution to the overall errors, so that correction for 1- and 2-body errors does not suffice to give a satisfactory description. For BLYP, a recent representation of 3-body energies due to Medders, Babin, and Paesani [J. Chem. Theory Comput. 9, 1103 (2013)] gives a reasonably good way of correcting for beyond-2-body errors, after which the remaining errors are typically 0.5 mE h ≃ 15 meV/monomer for the liquid and the

  15. Critical difference between optoelectronic properties of α- and β-SnWO4semiconductors: A DFT/HSE06 and experimental investigation

    KAUST Repository

    Harb, Moussab; Ziani, Ahmed; Takanabe, Kazuhiro

    2016-01-01

    The optoelectronic properties of β-SnWO4 are investigated in details using experiments on thin film generated by rapid quenching and the first-principles quantum calculations based on the density functional theory (DFT, including the perturbation

  16. Benchmark CCSD(T) and DFT study of binding energies in Be7 - 12: in search of reliable DFT functional for beryllium clusters

    Science.gov (United States)

    Labanc, Daniel; Šulka, Martin; Pitoňák, Michal; Černušák, Ivan; Urban, Miroslav; Neogrády, Pavel

    2018-05-01

    We present a computational study of the stability of small homonuclear beryllium clusters Be7 - 12 in singlet electronic states. Our predictions are based on highly correlated CCSD(T) coupled cluster calculations. Basis set convergence towards the complete basis set limit as well as the role of the 1s core electron correlation are carefully examined. Our CCSD(T) data for binding energies of Be7 - 12 clusters serve as a benchmark for performance assessment of several density functional theory (DFT) methods frequently used in beryllium cluster chemistry. We observe that, from Be10 clusters on, the deviation from CCSD(T) benchmarks is stable with respect to size, and fluctuating within 0.02 eV error bar for most examined functionals. This opens up the possibility of scaling the DFT binding energies for large Be clusters using CCSD(T) benchmark values for smaller clusters. We also tried to find analogies between the performance of DFT functionals for Be clusters and for the valence-isoelectronic Mg clusters investigated recently in Truhlar's group. We conclude that it is difficult to find DFT functionals that perform reasonably well for both beryllium and magnesium clusters. Out of 12 functionals examined, only the M06-2X functional gives reasonably accurate and balanced binding energies for both Be and Mg clusters.

  17. 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.

  18. NMR, MP2 and DFT Study of Thiophenoxyketenimines (o-ThioSchiff bases)

    DEFF Research Database (Denmark)

    Saeed, Bahjat Ali; Elias, Rita Sabah; Kamounah, Fadhil S.

    2018-01-01

    Five new thiophenoxyketinimines have been synthesized. 1 H and 13 C NMR spectra as well as deuterium isotope effects on 13 C chemical shifts are determined, and spectra are assigned. DFT and MP2 calculations of both structures, chemical shifts, and isotope effects on chemical shifts are done...... that calculations at the MP2 level are best to obtain correct "C═S" chemical shifts....

  19. 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.

  20. Error compensation of IQ modulator using two-dimensional DFT

    Energy Technology Data Exchange (ETDEWEB)

    Ohshima, Takashi, E-mail: ohshima@spring8.or.jp [RIKEN, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Maesaka, Hirokazu [RIKEN, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan); Matsubara, Shinichi [Japan Synchrotron Radiation Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Otake, Yuji [RIKEN, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2016-06-01

    It is important to precisely set and keep the phase and amplitude of an rf signal in the accelerating cavity of modern accelerators, such as an X-ray Free Electron Laser (XFEL) linac. In these accelerators an acceleration rf signal is generated or detected by an In-phase and Quadrature (IQ) modulator, or a demodulator. If there are any deviations of the phase and the amplitude from the ideal values, crosstalk between the phase and the amplitude of the output signal of the IQ modulator or the demodulator arises. This causes instability of the feedback controls that simultaneously stabilize both the rf phase and the amplitude. To compensate for such deviations, we developed a novel compensation method using a two-dimensional Discrete Fourier Transform (DFT). Because the observed deviations of the phase and amplitude of an IQ modulator involve sinusoidal and polynomial behaviors on the phase angle and the amplitude of the rf vector, respectively, the DFT calculation with these basis functions makes a good approximation with a small number of compensation coefficients. Also, we can suppress high-frequency noise components arising when we measure the deviation data. These characteristics have advantages compared to a Look Up Table (LUT) compensation method. The LUT method usually demands many compensation elements, such as about 300, that are not easy to treat. We applied the DFT compensation method to the output rf signal of a C-band IQ modulator at SACLA, which is an XFEL facility in Japan. The amplitude deviation of the IQ modulator after the DFT compensation was reduced from 15.0% at the peak to less than 0.2% at the peak for an amplitude control range of from 0.1 V to 0.9 V (1.0 V full scale) and for a phase control range from 0 degree to 360 degrees. The number of compensation coefficients is 60, which is smaller than that of the LUT method, and is easy to treat and maintain.

  1. Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: A DFT proposed mechanism

    KAUST Repository

    Solá ns, Xavier Luis; Chow, Catherine; Gouré , Eric; Kaya, Yasemin; Basset, Jean-Marie; Taoufik, Mostafa; Quadrelli, Elsje Alessandra; Eisenstein, Odile

    2012-01-01

    DFT(B3PW91) calculations have been carried out to propose a pathway for the N2 cleavage by H2 in the presence of silica-supported tantalum hydride complexes [(≡ SiO)2TaHx] that forms [(≡SiO)2Ta(NH)(NH2)] (Science2007, 317, 1056). The calculations

  2. 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.

  3. Ethylene dissociation on flat and stepped Ni(111): A combined STM and DFT study

    DEFF Research Database (Denmark)

    Vang, R.T.; Honkala, Johanna Karoliina; Dahl, S.

    2006-01-01

    The dissociative adsorption of ethylene (C(2)H(4)) on Ni(111) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites...... are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (111) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges. DFT calculations were performed for several intermediate steps...... in the decomposition of ethylene on both Ni(111) and the stepped Ni(211) surface. In general the Ni(211) surface is found to have a higher reactivity than the Ni(111) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular...

  4. Calculations of Changes in Reactivity during some regular periods of operation of JEN-1 MOD Reactor; Calculo de vairaciones de reactividad en algunos periodos regulares de operacion del reactor JEN-1 Mod.

    Energy Technology Data Exchange (ETDEWEB)

    Alcala Ruiz, F

    1973-07-01

    By a Point-Reactor model and Perturbation Theory, changes in reactivity during some regular operating periods of JEN-1 MOD Reactor have been calculated and compared with available measured values. they were in good agreement. Also changes in reactivity have been calculated during operations at higher power levels than the present one, concluding some practical consequences for the case of increasing the present power of this reactor. (Author)

  5. Probing the molecular and electronic structure of the lichen metabolite usnic acid: A DFT study

    International Nuclear Information System (INIS)

    Galasso, V.

    2010-01-01

    Graphical abstract: DFT calculations of structural preferences, acidic properties, carbonyl vibrations, 13 C NMR chemical shifts, and absorption spectrum account for the unique structural backbone, chemical behaviour, and spectroscopic properties of usnic acid, the cortical pigment and potent reactive of lichens. - Abstract: The molecular structure of usnic acid was investigated by the density functional theory (DFT). Two keto-enol tautomers are nearly isoenergetic and more stable than other tautomers. Noteworthy is the energy difference among the three intramolecular O-H...O hydrogen bonds. The DFT/PCM calculated dissociation constants account for the acidic sequence of the three OH-groups. The electronic structure was also studied by calculating IR/Raman, NMR, and absorption features. A reliable assignment of the 'fingerprint' carbonyl stretching modes was supported by calculations on related molecules. The calculated NMR chemical shifts fit expectation in terms of a fast interconversion between the two most preferred tautomers. A variety of π → π* and n → π* excitations, localized on a single ring or involving a charge-transfer between the two lateral rings of the molecule, gives rise to the broad UV-absorption bands. This property accounts for the efficient protection against damaging solar radiation provided by usnic acid for lichens.

  6. Probing the molecular and electronic structure of the lichen metabolite usnic acid: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Galasso, V., E-mail: galasso@univ.trieste.it [Dipartimento di Scienze Chimiche, Universita di Trieste, I-34127 Trieste (Italy)

    2010-08-23

    Graphical abstract: DFT calculations of structural preferences, acidic properties, carbonyl vibrations, {sup 13}C NMR chemical shifts, and absorption spectrum account for the unique structural backbone, chemical behaviour, and spectroscopic properties of usnic acid, the cortical pigment and potent reactive of lichens. - Abstract: The molecular structure of usnic acid was investigated by the density functional theory (DFT). Two keto-enol tautomers are nearly isoenergetic and more stable than other tautomers. Noteworthy is the energy difference among the three intramolecular O-H...O hydrogen bonds. The DFT/PCM calculated dissociation constants account for the acidic sequence of the three OH-groups. The electronic structure was also studied by calculating IR/Raman, NMR, and absorption features. A reliable assignment of the 'fingerprint' carbonyl stretching modes was supported by calculations on related molecules. The calculated NMR chemical shifts fit expectation in terms of a fast interconversion between the two most preferred tautomers. A variety of {pi} {yields} {pi}* and n {yields} {pi}* excitations, localized on a single ring or involving a charge-transfer between the two lateral rings of the molecule, gives rise to the broad UV-absorption bands. This property accounts for the efficient protection against damaging solar radiation provided by usnic acid for lichens.

  7. Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom

    Science.gov (United States)

    Baseden, Kyle A.; Tye, Jesse W.

    2014-01-01

    Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…

  8. Localized-overlap approach to calculations of intermolecular interactions

    Science.gov (United States)

    Rob, Fazle

    Symmetry-adapted perturbation theory (SAPT) based on the density functional theory (DFT) description of the monomers [SAPT(DFT)] is one of the most robust tools for computing intermolecular interaction energies. Currently, one can use the SAPT(DFT) method to calculate interaction energies of dimers consisting of about a hundred atoms. To remove the methodological and technical limits and extend the size of the systems that can be calculated with the method, a novel approach has been proposed that redefines the electron densities and polarizabilities in a localized way. In the new method, accurate but computationally expensive quantum-chemical calculations are only applied for the regions where it is necessary and for other regions, where overlap effects of the wave functions are negligible, inexpensive asymptotic techniques are used. Unlike other hybrid methods, this new approach is mathematically rigorous. The main benefit of this method is that with the increasing size of the system the calculation scales linearly and, therefore, this approach will be denoted as local-overlap SAPT(DFT) or LSAPT(DFT). As a byproduct of developing LSAPT(DFT), some important problems concerning distributed molecular response, in particular, the unphysical charge-flow terms were eliminated. Additionally, to illustrate the capabilities of SAPT(DFT), a potential energy function has been developed for an energetic molecular crystal of 1,1-diamino-2,2-dinitroethylene (FOX-7), where an excellent agreement with the experimental data has been found.

  9. 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.

  10. Using PWE/FE method to calculate the band structures of the semi-infinite beam-like PCs: Periodic in z-direction and finite in x–y plane

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Denghui, E-mail: qdhsd318@163.com; Shi, Zhiyu, E-mail: zyshi@nuaa.edu.cn

    2017-05-03

    This paper couples the plane wave expansion (PWE) and finite element (FE) methods to calculate the band structures of the semi-infinite beam-like phononic crystals (PCs) with the infinite periodicity in z-direction and finiteness in x–y plane. Explicit matrix formulations are developed for the calculation of band structures. In order to illustrate the applicability and accuracy of the proposed coupled plane wave expansion and finite element (PWE/FE) method to beam-like PCs, several examples are displayed. At first, PWE/FE method is applied to calculate the band structures of the Pb/rubber beam-like PCs with circular and rectangular cross sections, respectively. Then, it is used to calculate the band structures of steel/epoxy and steel/aluminum beam-like PCs with the same geometric parameters. Last, the band structure of the three-component beam-like PC is also calculated by the proposed method. Moreover, all the results calculated by PWE/FE method are compared with those calculated by finite element (FE) method, and the corresponding results are in good agreement. - Highlights: • The concept of the semi-infinite beam-like phononic crystals (PCs) is proposed. • The PWE/FE method is proposed and formulized to calculate the band structures of the semi-infinite beam-like PCs. • The strong applicability and high accuracy of PWE/FE method are verified.

  11. Ambient Levels of Primary and Secondary Pollutants in a Residential Area: Population Risk and Hazard Index Calculation over a Three Years Study Period

    OpenAIRE

    S. Al-Salem; A. Al-Fadhlee

    2007-01-01

    This paper aims at presenting data collected over the period of three years (2004-2006) in a residential area in the state of Kuwait. The data collected include ambient levels of primary and secondary pollutants with a number of metrological parameters. A series of unfiltered and filtered concentration roses were plotted to determine the predominant sources as well as the prevailing winds affecting the area under investigation. Local and international air quality regulations were cross refere...

  12. On the Necessity of Using Element No.155 in the Chemical Physical Calculations: Again on the Upper Limit in the Periodic Table of Elements

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2010-10-01

    Full Text Available It is shown how the properties of different elements of the Periodic System of Elements can be obtained using the properties of the theoretically predicted heaviest element No.155 (it draws the upper principal limit of the Table, behind which stable elements cannot exist. It is suggested how the properties of element No.155 can be used in the synthesis of superheavy elements. An analysis of nuclear reactions is also produced on the same basis.

  13. The power of joint application of LEED and DFT in quantitative surface structure determination

    International Nuclear Information System (INIS)

    Heinz, K; Hammer, L; Mueller, S

    2008-01-01

    It is demonstrated for several cases that the joint application of low-energy electron diffraction (LEED) and structural calculations using density functional theory (DFT) can retrieve the correct surface structure even though single application of both methods fails. On the experimental side (LEED) the failure can be due to the simultaneous presence of weak and very strong scatterers or to an insufficient data base leaving different structures with the same quality of fit between experimental data and calculated model intensities. On the theory side (DFT) it can be difficult to predict the coverage of an adsorbate or two different structures may own almost the same total energy, but only one of the structures is assumed in experiment due to formation kinetics. It is demonstrated how in the different cases the joint application of both methods-which yield about the same structural precision-offers a way out of the dilemma

  14. Benchmarking Hydrogen and Carbon NMR Chemical Shifts at HF, DFT, and MP2 Levels.

    Science.gov (United States)

    Flaig, Denis; Maurer, Marina; Hanni, Matti; Braunger, Katharina; Kick, Leonhard; Thubauville, Matthias; Ochsenfeld, Christian

    2014-02-11

    An extensive study of error distributions for calculating hydrogen and carbon NMR chemical shifts at Hartree-Fock (HF), density functional theory (DFT), and Møller-Plesset second-order perturbation theory (MP2) levels is presented. Our investigation employs accurate CCSD(T)/cc-pVQZ calculations for providing reference data for 48 hydrogen and 40 carbon nuclei within an extended set of chemical compounds covering a broad range of the NMR scale with high relevance to chemical applications, especially in organic chemistry. Besides the approximations of HF, a variety of DFT functionals, and conventional MP2, we also present results with respect to a spin component-scaled MP2 (GIAO-SCS-MP2) approach. For each method, the accuracy is analyzed in detail for various basis sets, allowing identification of efficient combinations of method and basis set approximations.

  15. OH-initiated transformation and hydrolysis of aspirin in AOPs system: DFT and experimental studies.

    Science.gov (United States)

    He, Lin; Sun, Xiaomin; Zhu, Fanping; Ren, Shaojie; Wang, Shuguang

    2017-08-15

    Advanced oxidation processes (AOPs) are widely used in wastewater treatment of pharmaceutical and personal care products (PPCPs). In this work, the OH-initiated transformation as well as the hydrolysis of a typical PPCPs, aspirin, was investigated using density functional theory (DFT) calculations and laboratory experiments. For DFT calculations, the frontier electron densities and bond dissociation energies were analyzed. Profiles of the potential energy surface were constructed, and all the possible pathways were discussed. Additionally, rate constants for each pathway were calculated with transition state theory (TST) method. UV/H 2 O 2 experiments of aspirin were performed and degradation intermediates were identified by UPLC-MS-MS analysis. Different findings from previous experimental works were reported that the H-abstraction pathways at methyl position were dominated and OH-addition pathways on benzene ring were also favored. Meantime, hydroxyl ASA was confirmed as the main stable intermediate. Moreover, it was the first time to use DFT method to investigate the hydrolysis mechanisms of organic ester compound. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. An Overview of the Adaptive Robust DFT

    Directory of Open Access Journals (Sweden)

    Djurović Igor

    2010-01-01

    Full Text Available Abstract This paper overviews basic principles and applications of the robust DFT (RDFT approach, which is used for robust processing of frequency-modulated (FM signals embedded in non-Gaussian heavy-tailed noise. In particular, we concentrate on the spectral analysis and filtering of signals corrupted by impulsive distortions using adaptive and nonadaptive robust estimators. Several adaptive estimators of location parameter are considered, and it is shown that their application is preferable with respect to non-adaptive counterparts. This fact is demonstrated by efficiency comparison of adaptive and nonadaptive RDFT methods for different noise environments.

  17. z-transform DFT filters and FFT's

    DEFF Research Database (Denmark)

    Bruun, G.

    1978-01-01

    The paper shows how discrete Fourier transformation can be implemented as a filter bank in a way which reduces the number of filter coefficients. A particular implementation of such a filter bank is directly related to the normal complex FFT algorithm. The principle developed further leads to types...... of DFT filter banks which utilize a minimum of complex coefficients. These implementations lead to new forms of FFT's, among which is acos/sinFFT for a real signal which only employs real coefficients. The new FFT algorithms use only half as many real multiplications as does the classical FFT....

  18. DFT study on dry reforming of methane over Ni2Fe overlayer of Ni(1 1 1) surface

    Science.gov (United States)

    Xu, Li-li; Wen, Hong; Jin, Xin; Bing, Qi-ming; Liu, Jing-yao

    2018-06-01

    We reported the complete catalytic cycle of dry reforming of methane (DRM) on Ni2Fe overlayer of Ni(1 1 1) surface by periodic density functional theory (DFT) calculations. The pathways for dehydrogenation of CH4 and CO2 activation were located. Our results demonstrate that compared with pure Ni(1 1 1) surface, the introduction Fe into Ni increases the energy barrier of CH dissociation to carbon and hydrogen atoms, thereby suppressing coke deposition on the surface, while it promotes the H-induced CO2 activation pathway to form OH radical, and thus not only the surface oxygen but also OH are responsible for the oxidation of CHx (x = 0,1) on the Ni2Fe overlayer. The most favorable pathway of CH/C oxidation is found to be CH∗ + OH∗ → CHOH∗ → CHO∗ + H∗ → CO∗ + 2H∗, with the rate-limiting energy barrier of 1.12 eV. Furthermore, since Fe is oxidized partially to FeO leading to a partial dealloying under DRM conditions, we also studied the surface-carbon removal and the activity for the reforming of methane on the FeO ribbon supported Ni(1 1 1) (FeO/Ni) interface by DFT+U method. The surface C reacts with lattice oxygen of FeO to produce CO via a Mars-van Krevelen (MvK) mechanism, with a very lower energy barrier of 0.16 eV. The present results show that the introduction of Fe into Ni has a positive effect on the activity toward DRM and has an improved coke resistance.

  19. Semiempirical and DFT computations of the influence of Tb(III) dopant on unit cell dimensions of cerium(III) fluoride.

    Science.gov (United States)

    Shyichuk, Andrii; Runowski, Marcin; Lis, Stefan; Kaczkowski, Jakub; Jezierski, Andrzej

    2015-01-30

    Several computational methods, both semiempirical and ab initio, were used to study the influence of the amount of dopant on crystal cell dimensions of CeF3 doped with Tb(3+) ions (CeF3 :Tb(3+) ). AM1, RM1, PM3, PM6, and PM7 semiempirical parameterization models were used, while the Sparkle model was used to represent the lanthanide cations in all cases. Ab initio calculations were performed by means of GGA+U/PBE projector augmented wave density functional theory. The computational results agree well with the experimental data. According to both computation and experiment, the crystal cell parameters undergo a linear decrease with increasing amount of the dopant. The computations performed using Sparkle/PM3 and DFT methods resulted in the best agreement with the experiment with the average deviation of about 1% in both cases. Typical Sparkle/PM3 computation on a 2×2×2 supercell of CeF3:Tb3+ lasted about two orders of magnitude shorter than the DFT computation concerning a unit cell of this material. © 2014 Wiley Periodicals, Inc.

  20. Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical.

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2016-06-21

    In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange-correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH(•) radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH(•) radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

  1. Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2016-01-01

    In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange–correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH • radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH • radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

  2. 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.

  3. DFT studies of hydrocarbon combustion on metal surfaces.

    Science.gov (United States)

    Arya, Mina; Mirzaei, Ali Akbar; Davarpanah, Abdol Mahmood; Barakati, Seyed Masoud; Atashi, Hossein; Mohsenzadeh, Abas; Bolton, Kim

    2018-02-02

    Catalytic combustion of hydrocarbons is an important technology to produce energy. Compared to conventional flame combustion, the catalyst enables this process to operate at lower temperatures; hence, reducing the energy required for efficient combustion. The reaction and activation energies of direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces were investigated using density functional theory (DFT). The data obtained for the Ag, Au, Al, Cu, Rh, Pt, and Pd surfaces were used to investigate the validity of the Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) relations for this reaction on these surfaces. These relations were found to be valid (R 2  = 0.94 for the BEP correlation and R 2  = 1.0 for the TSS correlation) and were therefore used to estimate the energetics of the combustion reaction on Ni, Co, and Fe surfaces. It was found that the estimated transition state and activation energies (E TS  = -69.70 eV and E a  = 1.20 eV for Ni, E TS  = -87.93 eV and E a  = 1.08 eV for Co and E TS  = -92.45 eV and E a  = 0.83 eV for Fe) are in agreement with those obtained by DFT calculations (E TS  = -69.98 eV and E a  = 1.23 eV for Ni, E TS  = -87.88 eV and E a  = 1.08 eV for Co and E TS  = -92.57 eV and E a  = 0.79 eV for Fe). Therefore, these relations can be used to predict energetics of this reaction on these surfaces without doing the time consuming transition state calculations. Also, the calculations show that the activation barrier for CH dissociation decreases in the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe.

  4. Electronic spectroscopy of HRe(CO) 5: a CASSCF/CASPT2 and TD-DFT study

    Science.gov (United States)

    Bossert, J.; Ben Amor, N.; Strich, A.; Daniel, C.

    2001-07-01

    The low-lying excited states of HRe(CO) 5 have been calculated at the CASSCF/CASPT2 and TD-DFT level of theory using relativistic effective core potentials (ECP) or ab initio model potentials (AIMP). The theoretical absorption spectrum is compared to the experimental one. Despite the similarity between the experimental absorption spectra of HMn(CO) 5 and HRe(CO) 5 in the UV/visible energy domain it is shown that the assignment differs significantly between the two molecules. The low-lying excited states of HRe(CO) 5 correspond to 5d→π *CO excitations whereas the spectrum of HMn(CO) 5 consists mainly of 3d→3d and 3d→ σ*Mn-H excitations. If the CASPT2 and TD-DFT results are quite comparable for the lowest excited states, the upper part assignment is more problematic with the TD-DFT method.

  5. Density functional theory (DFT) as a powerful tool for designing new organic corrosion inhibitors. Part 1: An overview

    International Nuclear Information System (INIS)

    Obot, I.B.; Macdonald, D.D.; Gasem, Z.M.

    2015-01-01

    The use of computational chemistry as a tool in the design and development of organic corrosion inhibitors has been greatly enhanced by the development of density functional theory (DFT). Whereas, traditionally, corrosion scientists have identified new corrosion inhibitor molecules either by incrementally changing the structures of existing inhibitors or by testing hundreds of compounds in the laboratory, these experimental means are often very expensive and time-consuming. Thus, ongoing hardware and software advances have opened the door for powerful use of theoretical chemistry in corrosion inhibition research at a reduced cost. DFT has enabled corrosion scientist to accurately predict the inhibition efficacies of organic corrosion inhibitors based on electronic/molecular properties and reactivity indices. This review summarizes the main features of DFT, giving a brief background to selected DFT-based chemical reactivity concepts, calculations and their applications to organic corrosion inhibitor design. The paper also reviews the principles upon which modern corrosion science is based with emphasis on corrosion in the oil and gas industry and with the goal of identifying important issues in the design of new, more effective inhibitors in this field. The impact of this review is to illustrate the enormous power of DFT and to identify shortcomings in past work, including the assumption that inhibitors only interact with bare metal surfaces.

  6. 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.

  7. Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions.

    Science.gov (United States)

    Vasilchenko, Danila B; Berdyugin, Semen N; Korenev, Sergey V; O'Kennedy, Sean; Gerber, Wilhelmus J

    2017-09-05

    The hydrolysis of [RhCl 6 ] 3- in NaOH-water solutions was studied by spectrophotometric methods. The reaction proceeds via successive substitution of chloride with hydroxide to quantitatively form [Rh(OH) 6 ] 3- . Ligand substitution kinetics was studied in an aqueous 0.434-1.085 M NaOH matrix in the temperature range 5.5-15.3 °C. Transformation of [RhCl 6 ] 3- into [RhCl 5 (OH)] 3- was found to be the rate-determining step with activation parameters of ΔH † = 105 ± 4 kJ mol -1 and ΔS † = 59 ± 10 J K -1 mol -1 . The coordinated hydroxo ligand(s) induces rapid ligand substitution to form [Rh(OH) 6 ] 3- . By simulating ligand substitution as a dissociative mechanism, using density functional theory (DFT), we can now explain the relatively fast and slow kinetics of chloride substitution in basic and acidic matrices, respectively. Moreover, the DFT calculated activation energies corroborated experimental data that the kinetic stereochemical sequence of [RhCl 6 ] 3- hydrolysis in an acidic solution proceeds as [RhCl 6 ] 3- → [RhCl 5 (H 2 O)] 2- → cis-[RhCl 4 (H 2 O) 2 ] - . However, DFT calculations predict in a basic solution the trans route of substitution [RhCl 6 ] 3- → [RhCl 5 (OH)] 3- → trans-[RhCl 4 (OH) 2 ] 3- is kinetically favored.

  8. A DFT+nonhomogeneous DMFT approach for finite systems

    International Nuclear Information System (INIS)

    Kabir, Alamgir; Turkowski, Volodymyr; Rahman, Talat S

    2015-01-01

    For reliable and efficient inclusion of electron–electron correlation effects in nanosystems we formulate a combined density functional theory/nonhomogeneous dynamical mean-field theory (DFT+DMFT) approach which employs an approximate iterated perturbation theory impurity solver. We further apply the method to examine the size-dependent magnetic properties of iron nanoparticles containing 11–100 atoms. We show that for the majority of clusters the DFT+DMFT solution is in very good agreement with experimental data, much better compared to the DFT and DFT+U results. In particular, it reproduces the oscillations in magnetic moment with size as observed experimentally. We thus demonstrate that the DFT+DMFT approach can be used for accurate and realistic description of nanosystems containing about hundred atoms. (paper)

  9. 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.

  10. 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

  11. 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.

  12. Diffusion of anthracene derivatives on Cu(111) studied by STM and DFT

    Science.gov (United States)

    Wyrick, Jonathan; Bartels, Ludwig; Einstein, Theodore

    2014-03-01

    Substituted anthracenes have drawn attention due to their ability to diffuse uniaxially on a Cu(111) surface. We compare anthracene to three of its derivatives whose 9,10 hydrogens are replaced by elements of the chalcogen group that act as linkers binding the molecules to a Cu(111) substrate. DFT calculations shed light on STM imaging and diffusion studies on the three substituted species. We present an analysis of the DFT results in which energetic contributions to the diffusion barriers are partitioned among the Kohn-Sham orbitals, allowing us to make assignments as to how each orbital affects diffusion for each species and draw comparisons between them. Present address: Center for Nanoscale Science and Technology, NIST, Gaithersburg, MD.

  13. DFT study of the structures and energetics of 98-atom AuPd clusters.

    Science.gov (United States)

    Bruma, Alina; Ismail, Ramli; Paz-Borbón, L Oliver; Arslan, Haydar; Barcaro, Giovanni; Fortunelli, Alessandro; Li, Z Y; Johnston, Roy L

    2013-01-21

    The energetics, structures and segregation of 98-atom AuPd nanoclusters are investigated using a genetic algorithm global optimization technique with the Gupta empirical potential (comparing three different potential parameterisations) followed by local minimizations using Density Functional Theory (DFT) calculations. A shell optimization program algorithm is employed in order to study the energetics of the highly symmetric Leary Tetrahedron (LT) structure and optimization of the chemical ordering of a number of structural motifs is carried out using the Basin Hopping Monte Carlo approach. Although one of the empirical potentials is found to favour the LT structure, it is shown that Marks Decahedral and mixed FCC-HCP motifs are lowest in energy at the DFT level.

  14. Screened coulomb hybrid DFT investigation of band gap and optical absorption predictions of CuVO3, CuNbO3 and Cu 5Ta11O30 materials

    KAUST Repository

    Harb, Moussab; Masih, Dilshad; Takanabe, Kazuhiro

    2014-01-01

    with high accuracy using advanced first-principles quantum methods based on DFT (including the perturbation theory approach DFPT) within the screened coulomb hybrid HSE06 exchange-correlation formalism. The calculated density of states are found

  15. 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.

  16. Combining DFT, Cluster Expansions, and KMC to Model Point Defects in Alloys

    Science.gov (United States)

    Modine, N. A.; Wright, A. F.; Lee, S. R.; Foiles, S. M.; Battaile, C. C.; Thomas, J. C.; van der Ven, A.

    In an alloy, defect energies are sensitive to the occupations of nearby atomic sites, which leads to a distribution of defect properties. When radiation-induced defects diffuse from their initially non-equilibrium locations, this distribution becomes time-dependent. The defects can become trapped in energetically favorable regions of the alloy leading to a diffusion rate that slows dramatically with time. Density Functional Theory (DFT) allows the accurate determination of ground state and transition state energies for a defect in a particular alloy environment but requires thousands of processing hours for each such calculation. Kinetic Monte-Carlo (KMC) can be used to model defect diffusion and the changing distribution of defect properties but requires energy evaluations for millions of local environments. We have used the Cluster Expansion (CE) formalism to ``glue'' together these seemingly incompatible methods. The occupation of each alloy site is represented by an Ising-like variable, and products of these variables are used to expand quantities of interest. Once a CE is fit to a training set of DFT energies, it allows very rapid evaluation of the energy for an arbitrary configuration, while maintaining the accuracy of the underlying DFT calculations. These energy evaluations are then used to drive our KMC simulations. We will demonstrate the application of our DFT/MC/KMC approach to model thermal and carrier-induced diffusion of intrinsic point defects in III-V alloys. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE.

  17. Structural studies on Mannich bases of 2-Hydroxy-3,4,5,6-tetrachlorobenzene. An UV, IR, NMR and DFT study. A mini-review

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Spanget-Larsen, Jens

    2016-01-01

    Mannich bases of 2-Hydroxy-3,4,5,6-tetrachlorobenzene are chosen as an exemplary case for tautomeric Mannich bases. Molecular structures are calculated. OH stretching frequencies are rationalized based on DFT calculations. Intrinsic deuterium isotope effects on 13C chemical shifts in the M-form a...

  18. IR and NMR spectroscopic correlation of enterobactin by DFT

    Science.gov (United States)

    Moreno, M.; Zacarias, A.; Porzel, A.; Velasquez, L.; Gonzalez, G.; Alegría-Arcos, M.; Gonzalez-Nilo, F.; Gross, E. K. U.

    2018-06-01

    Emerging and re-emerging epidemic diseases pose an ongoing threat to global health. Currently, Enterobactin and Enterobactin derivatives have gained interest, owing to their potential application in the pharmaceutical field. As it is known [J. Am. Chem. Soc (1979) 101, 20, 6097-6104], Enterobactin (H6EB) is an efficient iron carrier synthesized and secreted by many microbial species. In order to facilitate the elucidation of enterobactin and its analogues, here we propose the creation of a H6EB standard set using Density Functional Theory Infrared (IR) and NMR spectra. We used two exchange-correlation (xc) functionals (PBE including long-range corrections sbnd LC-PBEsbnd and mPW1), 2 basis sets (QZVP and 6-31G(d)) and 2 grids (fine and ultrafine) for most of the H6EB structures dependent of dihedral angles. The results show a significant difference between the Osbnd H and Nsbnd H bands, while the Cdbnd O amide and Osbnd (Cdbnd O)sbnd IR bands are often found on top of each other. The NMR DFT calculations show a strong dependence on the xc functional, basis set, and grid used for the H6EB structure. Calculated 1H and 13C NMR spectra enable the effect of the solvent to be understood in the context of the experimental measurements. The good agreement between the experimental and the calculated spectra using LC-PBE/QZVP and ultrafine grid suggest the possibility of the systems reported here to be considered as a standard set. The dependence of electrostatic potential and frontier orbitals with the catecholamide dihedral angles of H6EB is described. The matrix-assisted laser desorption/ionization time of the flight mass spectrometry (MALDI-TOF MS) of H6EB is also reported of manner to enrich the knowledge about its reactivity.

  19. DFT application for chlorin derivatives photosensitizer drugs modeling

    Science.gov (United States)

    Machado, Neila; Carvalho, B. G.; Téllez Soto, C. A.; Martin, A. A.; Favero, P. P.

    2018-04-01

    Photodynamic therapy is an alternative form of cancer treatment that meets the desire for a less aggressive approach to the body. It is based on the interaction between a photosensitizer, activating light, and molecular oxygen. This interaction results in a cascade of reactions that leads to localized cell death. Many studies have been conducted to discover an ideal photosensitizer, which aggregates all the desirable characteristics of a potent cell killer and generates minimal side effects. Using Density Functional Theory (DFT) implemented in the program Vienna Ab-initio Simulation Package, new chlorin derivatives with different functional groups were simulated to evaluate the different absorption wavelengths to permit resonant absorption with the incident laser. Gaussian 09 program was used to determine vibrational wave numbers and Natural Bond Orbitals. The chosen drug with the best characteristics for the photosensitizer was a modified model of the original chlorin, which was called as Thiol chlorin. According to our calculations it is stable and is 19.6% more efficient at optical absorption in 708 nm in comparison to the conventional chlorin e6. Vibrational modes, optical and electronic properties were predicted. In conclusion, this study is an attempt to improve the development of new photosensitizer drugs through computational methods that save time and contribute to decrease the numbers of animals for model application.

  20. Low-lying excited states by constrained DFT

    Science.gov (United States)

    Ramos, Pablo; Pavanello, Michele

    2018-04-01

    Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, Nc, in the virtual space of a reference set of occupied orbitals. By imposing this population to be Nc = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

  1. A computational DFT study of structural transitions in textured solid-fluid interfaces

    Science.gov (United States)

    Yatsyshin, Petr; Parry, Andrew O.; Kalliadasis, Serafim

    2015-11-01

    Fluids adsorbed at walls, in capillary pores and slits, and in more exotic, sculpted geometries such as grooves and wedges can exhibit many new phase transitions, including wetting, pre-wetting, capillary-condensation and filling, compared to their bulk counterparts. As well as being of fundamental interest to the modern statistical mechanical theory of inhomogeneous fluids, these are also relevant to nanofluidics, chemical- and bioengineering. In this talk we will show using a microscopic Density Functional Theory (DFT) for fluids how novel, continuous, interfacial transitions associated with the first-order prewetting line, can occur on steps, in grooves and in wedges, that are sensitive to both the range of the intermolecular forces and interfacial fluctuation effects. These transitions compete with wetting, filling and condensation producing very rich phase diagrams even for relatively simple geometries. We will also discuss practical aspects of DFT calculations, and demonstrate how this statistical-mechanical framework is capable of yielding complex fluid structure, interfacial tensions, and regions of thermodynamic stability of various fluid configurations. As a side note, this demonstrates that DFT is an excellent tool for the investigations of complex multiphase systems. We acknowledge financial support from the European Research Council via Advanced Grant No. 247031.

  2. Tetramer model of leukoemeraldine-emeraldine electrochemistry in the presence of trihalogenoacetic acids. DFT approach.

    Science.gov (United States)

    Barbosa, Nuno Almeida; Grzeszczuk, Maria; Wieczorek, Robert

    2015-01-15

    First results of the application of the DFT computational approach to the reversible electrochemistry of polyaniline are presented. A tetrameric chain was used as the simplest model of the polyaniline polymer species. The system under theoretical investigation involved six tetramer species, two electrons, and two protons, taking part in 14 elementary reactions. Moreover, the tetramer species were interacting with two trihalogenoacetic acid molecules. Trifluoroacetic, trichloroacetic, and tribromoacetic acids were found to impact the redox transformation of polyaniline as shown by cyclic voltammetry. The theoretical approach was considered as a powerful tool for investigating the main factors of importance for the experimental behavior. The DFT method provided molecular structures, interaction energies, and equilibrium energies of all of the tetramer-acid complexes. Differences between the energies of the isolated tetramer species and their complexes with acids are discussed in terms of the elementary reactions, that is, ionization potentials and electron affinities, equilibrium constants, electrode potentials, and reorganization energies. The DFT results indicate a high impact of the acid on the reorganization energy of a particular elementary electron-transfer reaction. The ECEC oxidation path was predicted by the calculations. The model of the reacting system must be extended to octamer species and/or dimeric oligomer species to better approximate the real polymer situation.

  3. Calculation of the dynamic first electronic hyperpolarizability β(−ω{sub σ}; ω{sub 1}, ω{sub 2}) of periodic systems. Theory, validation, and application to multi-layer MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Maschio, Lorenzo, E-mail: lorenzo.maschio@unito.it; Dovesi, Roberto [Dipartimento di Chimica and NIS (Nanostructured Interfaces and Surfaces) Centre, Università di Torino, via Giuria 5, I-10125 Torino (Italy); Rérat, Michel [Equipe de Chimie Physique, IPREM UMR5254, Université de Pau et des Pays de l’Adour, 64000 Pau (France); Kirtman, Bernard [Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States)

    2015-12-28

    We describe our implementation of a fully analytical scheme, based on the 2n + 1 rule, for computing the coupled perturbed Hartree Fock and Kohn-Sham dynamic first hyperpolarizability tensor β(−ω{sub σ}; ω{sub 1}, ω{sub 2}) of periodic 1D (polymer), 2D (slab), and 3D (crystal) systems in the CRYSTAL code [R. Dovesi et al., Int. J. Quantum Chem. 114, 1287 (2014)], which utilizes local Gaussian type basis sets. The dc-Pockels (dc-P) and second harmonic generation (SHG) tensors are included as special cases. It is verified that (i) symmetry requirements are satisfied; (ii) using LiF as an example, the infinite periodic polymer result agrees with extrapolated finite oligomer calculations and, likewise, for the build-up to a 2D slab and a 3D crystal; (iii) the values converge to the static case for low frequencies; and (iv) the Bishop-deKee dispersion formulas relating dc-P, SHG, and general processes are reproduced through quartic terms. Preliminary SHG calculations on multi-layer MoS{sub 2} satisfactorily reproduce experimental data.

  4. Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2 ] ↔ [Ni-NO] redox couple using DFT methods.

    Science.gov (United States)

    Tsipis, Athanassios C

    2017-07-15

    The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H-atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO 2 )(S 2 CNHMe)(PMe 3 )] ⇌ [Ni( κO,O2-ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  5. SERS and DFT study of p-hydroxybenzoic acid adsorbed on colloidal silver particles.

    Science.gov (United States)

    Chen, Y; Chen, S J; Li, S; Wei, J J

    2015-10-16

    In this study, normal Raman spectra of p—hydroxybenzoic acid (PHBA) powder and its surface—enhanced Raman scattering (SERS) spectra in silver colloidal solutions were measured under near infrared excitation conditions. In theoretical calculation, two models of PHBA adsorbed on the surfaces of silver nanoparticles were established. The Raman frequencies of these two models using density functional theory (DFT) method were calculated, and compared with the experimental results. It was found that the calculated Raman frequencies were in good agreement with experimental values, which indicates that there are two enhanced mechanism physical (electromagnetic, EM) enhancement and chemical (charge—transfer, CT) enhancement, in silver colloidal solutions regarding SERS effect. Furthermore, from high—quality SERS spectrum of PHBA obtained in silver colloids, we inferred that PHBA molecules in silver colloids adsorb onto the metal surfaces through carboxyl at a perpendicular orientation. The combination of SERS spectra and DFT calculation is thus useful for studies of the adsorption—orientation of a molecule on a metal colloid.

  6. Redesign of the DFT/MRCI Hamiltonian

    Energy Technology Data Exchange (ETDEWEB)

    Lyskov, Igor; Kleinschmidt, Martin; Marian, Christel M., E-mail: Christel.Marian@hhu.de [Institute of Theoretical and Computational Chemistry, Heinrich-Heine-University Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf (Germany)

    2016-01-21

    The combined density functional theory and multireference configuration interaction (DFT/MRCI) method of Grimme and Waletzke [J. Chem. Phys. 111, 5645 (1999)] is a well-established semi-empirical quantum chemical method for efficiently computing excited-state properties of organic molecules. As it turns out, the method fails to treat bi-chromophores owing to the strong dependence of the parameters on the excitation class. In this work, we present an alternative form of correcting the matrix elements of a MRCI Hamiltonian which is built from a Kohn-Sham set of orbitals. It is based on the idea of constructing individual energy shifts for each of the state functions of a configuration. The new parameterization is spin-invariant and incorporates less empirism compared to the original formulation. By utilizing damping techniques together with an algorithm of selecting important configurations for treating static electron correlation, the high computational efficiency has been preserved. The robustness of the original and redesigned Hamiltonians has been tested on experimentally known vertical excitation energies of organic molecules yielding similar statistics for the two parameterizations. Besides that, our new formulation is free from artificially low-lying doubly excited states, producing qualitatively correct and consistent results for excimers. The way of modifying matrix elements of the MRCI Hamiltonian presented here shall be considered as default choice when investigating photophysical processes of bi-chromophoric systems such as singlet fission or triplet-triplet upconversion.

  7. Understanding and Calibrating Density-Functional-Theory Calculations Describing the Energy and Spectroscopy of Defect Sites in Hexagonal Boron Nitride.

    Science.gov (United States)

    Reimers, Jeffrey R; Sajid, A; Kobayashi, Rika; Ford, Michael J

    2018-03-13

    Defect states in 2-D materials present many possible uses but both experimental and computational characterization of their spectroscopic properties is difficult. We provide and compare results from 13 DFT and ab initio computational methods for up to 25 excited states of a paradigm system, the V N C B defect in hexagonal boron nitride (h-BN). Studied include: (i) potentially catastrophic effects for computational methods arising from the multireference nature of the closed-shell and open-shell states of the defect, which intrinsically involves broken chemical bonds, (ii) differing results from DFT and time-dependent DFT (TDDFT) calculations, (iii) comparison of cluster models to periodic-slab models of the defect, (iv) the starkly differing effects of nuclear relaxation on the various electronic states that control the widths of photoabsorption and photoemission spectra as broken bonds try to heal, (v) the effect of zero-point energy and entropy on free-energy differences, (vi) defect-localized and conduction/valence-band transition natures, and (vii) strategies needed to ensure that the lowest-energy state of a defect can be computationally identified. Averaged state-energy differences of 0.3 eV are found between CCSD(T) and MRCI energies, with thermal effects on free energies sometimes also being of this order. However, DFT-based methods can perform very poorly. Simple generalized-gradient functionals like PBE fail at the most basic level and should never be applied to defect states. Hybrid functionals like HSE06 work very well for excitations within the triplet manifold of the defect, with an accuracy equivalent to or perhaps exceeding the accuracy of the ab initio methods used. However, HSE06 underestimates triplet-state energies by on average of 0.7 eV compared to closed-shell singlet states, while open-shell singlet states are predicted to be too low in energy by 1.0 eV. This leads to misassignment of the ground state of the V N C B defect. Long

  8. Study of Calculation Method on Concession Period of PPP Project in Mixed Financing Mode%混合融资的PPP项目特许期计算方法研究

    Institute of Scientific and Technical Information of China (English)

    张芳; 马金平; 靳小青

    2015-01-01

    It is an important measure to lead the private capital to invest on infrastructure construction for the reform of financing structure in fixed assets in China,which makes the financing mode transmit from state single investment to multilateral co-investment. Therefore,it is of great practical significance to explore the problem of calculating the concession period of PPP project in the mixed financing mode. According to the financial management theory,this paper puts forward the calculation method of concession period based on the definition of the concession period,which can determine the concession period for different proportions of contribution and the private gains should be allocated according to the preset proportions. An example is provided to illustrate the application procedure of the method,and verify the reliability and applicability of the proposed method,which provides a reference for determining the concession period in mixed financing mode. This paper also points out the limitation and the future direction of the study.%引导民营资本投入基础设施建设领域是我国改革固定资产投融资结构的一项重要举措,使得我国基础设施建设的融资模式由过去的单一国家投资改为多方共同投资的混合融资模式。因此,探索混合融资模式下的 PPP 项目特许期如何计算的问题具有重要的现实意义。在对特许期的概念进行界定的基础上,根据财务管理理论提出了特许期计算方法。该方法可针对各方的不同投资比例,对在民营期内项目获得的收益,按预设分配比例进行分配的前提下,计算 PPP 项目的特许期。通过对实际案例的分析,说明了计算方法的应用过程,验证了方法的可靠性与适用性,这对于解决混合融资模式下特许期的计算问题具有较大的参考价值。

  9. 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.

  10. The influence of the dispersion corrections on the performance of DFT method in modeling HNgY noble gas molecules and their complexes

    Science.gov (United States)

    Cukras, Janusz; Sadlej, Joanna

    2018-01-01

    The letter reports a comparative assessment of the usefulness of the two different Grimme's corrections for evaluating dispersion interaction (DFT-D3 and DFT-D3BJ) for the representative molecules of the family of noble-gas hydrides HXeY and their complexes with the HZ molecules, where Y and Z are F/Cl/OH/SH. with special regard to the dispersion term calculated by means of the symmetry-adapted perturbation theory (at the SAPT0 level). The results indicate that despite differences in the total interactions energy (DFT + corrections) versus SAPT0 results, the sequence of contributions of the individual dispersion terms is still maintained. Both dispersion corrections perform similarly and they improve the results suggesting that it is worthwhile to include them in calculations.

  11. A combined semiempirical-DFT study of oligomers within the finite-chain approximation, evolution from oligomers to polymers.

    Science.gov (United States)

    Derosa, Pedro A

    2009-06-01

    A computationally cheap approach combining time-independent density functional theory (TIDFT) and semiempirical methods with an appropriate extrapolation procedure is proposed to accurately estimate geometrical and electronic properties of conjugated polymers using just a small set of oligomers. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap (HLG) obtained at a TIDFT level (B3PW91) for two polymers, trans-polyacetylene--the simplest conjugated polymer, and a much larger poly(2-methoxy-5-(2,9-ethyl-hexyloxy)-1,4-phenylenevinylene (MEH-PPV) polymer converge to virtually the same asymptotic value than the excitation energy obtained with time-dependent DFT (TDDFT) calculations using the same functional. For TIDFT geometries, the HLG is found to converge to a value within the experimentally accepted range for the band gap of these polymers, when an exponential extrapolation is used; however if semiempirical geometries are used, a linear fit of the HLG versus 1/n is found to produce the best results. Geometrical parameters are observed to reach a saturation value in good agreement with experimental information, within the length of oligomers calculated here and no extrapolation was considered necessary. Finally, the performance of three different semiempirical methods (AM1, PM3, and MNDO) and for the TIDFT calculations, the performance of 7 different full electron basis sets (6-311+G**, 6-31+ +G**, 6-311+ +G**, 6-31+G**, 6-31G**, 6-31+G*, and 6-31G) is compared and it is determined that the choice of semiempirical method or the basis set does not significantly affect the results. 2008 Wiley Periodicals, Inc.

  12. 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

  13. 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.

  14. 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...

  15. 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.

  16. 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.

  17. (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.

  18. Vibrational analysis and thermodynamic properties of C120 nanotorus: a DFT study

    International Nuclear Information System (INIS)

    López-Chávez, Ernesto; Cruz-Torres, Armando; Landa Castillo-Alvarado, Fray de; Ortíz-López, Jaime; Peña-Castañeda, Yésica A.; Martínez-Magadán, José Manuel

    2011-01-01

    Density functional theory (DFT) computational methods are applied to a C 120 carbon nanotorus studied as an isolated molecular species, using the functional GGA PW91. This toroidal form of carbon contains five fold, six fold, and sevenfold rings. The calculated cohesive energy of the nanotorus, indicates that the ground state of this structure is energetically more stable than that of fullerene C 60 . Geometry and stability, Raman and IR vibrational analysis and thermodynamic properties have been reported and compared to the values obtained by other authors.

  19. Thermal properties of black phosphorene and doped phosphorene (C, N & O): A DFT study

    Science.gov (United States)

    Devi, Anjna; Singh, Amarjeet

    2018-04-01

    In this work, we present the results from a DFT based computational study of pristine phosphorene and doped (C, N & O) phosphorene. We systematically investigated the lattice thermal properties of black phosphorene and the effect of doping on its thermal properties. We first determined the vibrational properties of pristine and doped phosphorene and from these results we calculated their thermal properties. We doped the phosphorene with C, N and O and observed that the structural stability of doped phosphorene decreases, while the thermal stability is increased as compared to pristine phosphorene. The presence of finite temperature effects in the doped system can contribute to acceleration of progress in future nano-scale technology.

  20. Combined MCD/DFT/TDDFT Study of the Electronic Structure of Axially Pyridine Coordinated Metallocorroles.

    Science.gov (United States)

    Rhoda, Hannah M; Crandall, Laura A; Geier, G Richard; Ziegler, Christopher J; Nemykin, Victor N

    2015-05-18

    A series of metallocorroles were investigated by UV-vis and magnetic circular dichroism spectroscopies. The diamagnetic distorted square-pyramidal main-group corrole Ga(tpfc)py (2), the diamagnetic distorted octahedral transition-metal adduct Co(tpfc)(py)2 (3), and paramagnetic distorted octahedral transition-metal complex Fe(tpfc)(py)2 (4) [H3tpfc = tris(perfluorophenyl)corrole] were studied to investigate similarities and differences in the electronic structure and spectroscopy of the closed- and open-shell metallocorroles. Similar to the free-base H3tpfc (1), inspection of the MCD Faraday B-terms for all of the macrocycles presented in this report revealed that a ΔHOMO MCD spectra. In addition, the MCD spectra of the cobalt and the iron complexes were also complicated by a number of charge-transfer states in the visible region. Iron complex 4 also exhibits a low-energy absorption in the NIR region (1023 nm). DFT and TDDFT calculations were used to elaborate the electronic structures and provide band assignments in UV-vis and MCD spectra of the metallocorroles. DFT and TDDFT calculations predict that the orientation of the axial pyridine ligand(s) has a very minor influence on the calculated electronic structures and absorption spectra in the target systems.

  1. 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.

  2. DFT study of structure, IR and Raman spectra of the fluorescent "Janus" dendron built from cyclotriphosphazene core

    Science.gov (United States)

    Furer, V. L.; Vandyukova, I. I.; Vandyukov, A. E.; Fuchs, S.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2011-11-01

    The FTIR and FT-Raman spectra of the zero generation dendron, possessing five fluorescent dansyl terminal groups, cyclotriphosphazene core, and one carbamate function G0v were studied. The structural optimization and normal mode analysis were performed for G0v dendron on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendron molecule G0v has a concave lens structure with slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of G0v dendron were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The frequency of ν(N-H) band in the IR spectrum reveal the presence of H-bonds in the G0v dendron.

  3. DFT theoretical investigations of π-conjugated molecules based on thienopyrazine and different acceptor moieties for organic photovoltaic cells

    Directory of Open Access Journals (Sweden)

    Mohammed Bourass

    2016-09-01

    Full Text Available In this work, theoretical study by using the DFT method on eleven conjugated compounds based on thienopyrazine is reported. Different electron side groups were introduced to investigate their effects on the electronic structure; The HOMO, LUMO and Gap energy of these compounds have been calculated and reported in this paper. A systematic theoretical study of such compound has not been reported as we know. Thus, our aim is first, to explore their electronic and spectroscopic properties on the basis of the DFT quantum chemical calculations. Second, we are interested to elucidate the parameters that influence the photovoltaic efficiency toward better understanding of the structure–property relationships. The study of structural, electronic and optical properties for these compounds could help to design more efficient functional photovoltaic organic materials.

  4. Overpotential for CO2 electroreduction lowered on strained penta-twinned Cu nanowires? ?Electronic supplementary information (ESI) available: Details of DFT and MD calculations, CHE model and reaction pathways for C2H4 production. See DOI: 10.1039/c5sc02667a Click here for additional data file.

    OpenAIRE

    Chen, Zhengzheng; Zhang, Xu; Lu, Gang

    2015-01-01

    Based on first-principles calculations, we predict that penta-twinned Cu nanowires (NWs) are superior to conventional Cu catalysts for CO2 electroreduction. The penta-twinned NWs possess a combination of ultrahigh mechanical strength, large surface-to-volume ratios and an abundance of undercoordinated adsorption sites, all desirable for CO2 electroreduction. In particular, we show that the penta-twinned Cu NWs can withstand elastic strains orders of magnitude higher than their conventional co...

  5. Calculations of optical rotation: Influence of molecular structure

    Directory of Open Access Journals (Sweden)

    Yu Jia

    2012-01-01

    Full Text Available Ab initio Hartree-Fock (HF method and Density Functional Theory (DFT were used to calculate the optical rotation of 26 chiral compounds. The effects of theory and basis sets used for calculation, solvents influence on the geometry and values of calculated optical rotation were all discussed. The polarizable continuum model, included in the calculation, did not improve the accuracy effectively, but it was superior to γs. Optical rotation of five or sixmembered of cyclic compound has been calculated and 17 pyrrolidine or piperidine derivatives which were calculated by HF and DFT methods gave acceptable predictions. The nitrogen atom affects the calculation results dramatically, and it is necessary in the molecular structure in order to get an accurate computation result. Namely, when the nitrogen atom was substituted by oxygen atom in the ring, the calculation result deteriorated.

  6. A new DFT approach to model small polarons in oxides with proper account for long-range polarization

    Science.gov (United States)

    Kokott, Sebastian; Levchenko, Sergey V.; Scheffler, Matthias; Theory Department Team

    In this work, we address two important challenges in the DFT description of small polarons (excess charges localized within one unit cell): sensitivity to the errors in exchange-correlation (XC) treatment and finite-size effects in supercell calculations. The polaron properties are obtained using a modified neutral potential-energy surface (PES). Using the hybrid HSE functional and considering the whole range 0 Deutsche Forschungsgemeinschaft).

  7. DFT, Its Impact on Condensed Matter and on ``Materials-Genome'' Research

    Science.gov (United States)

    Scheffler, Matthias

    About 40 years ago, two seminal works demonstrated the power of density-functional theory (DFT) for real materials. These studies by Moruzzi, Janak, and Williams on metals and Yin and Cohen on semiconductors visualized the spatial distribution of electrons, predicted the equation of state of solids, crystal stability, pressure-induced phase transitions, and more. They also stressed the importance of identifying trends by looking at many systems (e.g. the whole transition-metal series). Since then, the field has seen numerous applications of DFT to solids, liquids, defects, surfaces, and interfaces providing important descriptions and explanations as well as predictions of experimentally not yet identified systems. - ∖ ∖ About 10 years ago, G. Ceder and his group [Ref. 3 and references therein] started with high-throughput screening calculations in the spirit of what in 2011 became the ``Materials Genome Initiative''. The idea of high-throughput screening is old (a key example is the ammonia catalyst found by A. Mittasch at BASF more than 100 years ago), but it is now increasingly becoming clear that big data of materials does not only provide direct information but that the data is structured. This enables interpolation, (modest) extrapolation, and new routes towards understanding [Ref. 5 and references therein]. - ∖ ∖ The amount of data created by ``computational materials science'' is significant. For instance, the NoMaD Repository (which includes also data from other repositories, e.g. AFLOWLIB and OQMD) now holds more than 18 million total-energy calculations. In fact, the amount of data of computational materials science is steadily increasing, and about hundred million CPU core hours are nowadays used every day, worldwide, for DFT calculations for materials. - ∖ ∖ The talk will summarize this enormous impact of DFT on materials science, and it will address the next steps, e.g. the issue how to exploit big data of materials for doing forefront

  8. 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.

  9. 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.

  10. Anatase-rutile phase transformation of titanium dioxide bulk material: a DFT + U approach

    International Nuclear Information System (INIS)

    Vu, Nam H; Le, Hieu V; Cao, Thi M; Pham, Viet V; Le, Hung M; Nguyen-Manh, Duc

    2012-01-01

    The anatase-rutile phase transformation of TiO 2 bulk material is investigated using a density functional theory (DFT) approach in this study. According to the calculations employing the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the Vanderbilt ultrasoft pseudopotential, it is suggested that the anatase phase is more energetically stable than rutile, which is in variance with the experimental observations. Consequently, the DFT + U method is employed in order to predict the correct structural stability in titania from electronic-structure-based total energy calculations. The Hubbard U term is determined by examining the band structure of rutile with various values of U from 3 to 10 eV. At U = 5 eV, a theoretical bandgap for rutile is obtained as 3.12 eV, which is in very good agreement with the reported experimental bandgap. Hence, we choose the DFT + U method (with U = 5 eV) to investigate the transformation pathway using the newly-developed solid-state nudged elastic band (ss-NEB) method, and consequently obtain an intermediate transition structure that is 9.794 eV per four-TiO 2 above the anatase phase. When the Ti-O bonds in the transition state are examined using charge density analysis, seven Ti-O bonds (out of 24 bonds in the anatase unit cell) are broken, and this result is in excellent agreement with a previous experimental study (Penn and Banfield 1999 Am. Miner. 84 871-6).

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Calculation of exchange coupling constants in triply-bridged dinuclear Cu(II) compounds based on spin-flip constricted variational density functional theory.

    Science.gov (United States)

    Seidu, Issaka; Zhekova, Hristina R; Seth, Michael; Ziegler, Tom

    2012-03-08

    The performance of the second-order spin-flip constricted variational density functional theory (SF-CV(2)-DFT) for the calculation of the exchange coupling constant (J) is assessed by application to a series of triply bridged Cu(II) dinuclear complexes. A comparison of the J values based on SF-CV(2)-DFT with those obtained by the broken symmetry (BS) DFT method and experiment is provided. It is demonstrated that our methodology constitutes a viable alternative to the BS-DFT method. The strong dependence of the calculated exchange coupling constants on the applied functionals is demonstrated. Both SF-CV(2)-DFT and BS-DFT affords the best agreement with experiment for hybrid functionals.

  16. Synthesis, characterization and DFT studies of two new silver(I) complexes with 3,4-lutidine

    Science.gov (United States)

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

    2015-04-01

    The synthesis, characterization and molecular structure of two new Ag(I) complexes with 3,4-lutidine (34lut) have been reported. The [Ag(34lut)3(OAC)]; 1 and [Ag(34lut)2(TFA)]; 2 complexes, where OAC and TFA are acetate and trifluoroacetate respectively, have been characterized using elemental analysis, FTIR, NMR and mass spectra. Their molecular structures were calculated using DFT quantum chemical calculations. Both 1 and 2 were found to have distorted tetrahedral geometry around the Ag(I). The spectroscopic properties of the studied complexes have been calculated using the same level of theory. The Infrared vibrational frequencies of the COO stretches confirmed that the OAC is monodentate in 1 while the TFA is bidentate in 2. The calculated polarizability (α0) and HOMO-LUMO energy gap (ΔE) values indicated that 1 has higher NLO activity than 2. The electronic spectra of these complexes are calculated using the TD-DFT calculations. The calculated 1H NMR chemical shift values using GIAO approach showed good correlations with the experimental data. The interaction energies using the second order perturbation theory have been used to study the different intramolecular charge transfer interactions in the studied complexes. The NBO calculations indicated that both the Agsbnd O bonds are almost identical in 2 but not in 1.

  17. Structural, electronic, mechanical, thermal and optical properties of B(P,As)1-xNx; (x = 0, 0.25, 0.5, 0.75, 1) alloys and hardness of B(P,As) under compression using DFT calculations

    Science.gov (United States)

    Viswanathan, E.; Sundareswari, M.; Jayalakshmi, D. S.; Manjula, M.; Krishnaveni, S.

    2017-09-01

    First principles calculations are carried out in order to analyze the structural, electronic, mechanical, thermal and optical properties of BP and BAs compounds by ternary alloying with nitrogen namely B(P,As)1-xNx (x = 0.25, 0.5, 0.75) alloys at ambient condition. Thereby we report the mechanical and thermal properties of B(P,As)1-xNx (x = 0.25, 0.5, 0.75) alloys namely bulk modulus, shear modulus, Young's modulus, hardness, ductile-brittle nature, elastic wave velocity, Debye temperature, melting point, etc.; optical properties of B(P)1-xNx (x = 0.25, 0.5, 0.75) and B(As)1-xNx (x = 0.25, 0.75) alloys namely the dielectric function of real and imaginary part, refractive index, extinction coefficient and reflectivity and the hardness profile of the parent compounds BP and BAs under compression. The charge density plot, density of states histograms and band structures are plotted and discussed for all the ternary alloys of the present study. The calculated results agree very well with the available literature. Analysis of the present study reveals that the ternary alloy combinations namely BP.25N.75 and BAs.25N.75 could be superhard materials; hardness of BP and BAs increases with compression.

  18. An approach based on genetic algorithms and DFT for studying clusters: (H2O) n (2 ≤ n ≤ 13) cluster analysis

    International Nuclear Information System (INIS)

    Sabato de Abreu e Silva, Elcio; Anderson Duarte, Helio; Belchior, Jadson Claudio

    2006-01-01

    The present work proposes the application of a genetic algorithm (GA) for determining global minima to be used as seeds for a higher level ab initio method analysis such as density function theory (DFT). Water clusters ((H 2 O) n (2 ≤ n ≤ 13)) are used as a test case and for the initial guesses four empirical potentials (TIP3P, TIP4P, TIP5P and ST2) were considered for the GA calculations. Two types of analysis were performed namely rigid (DFT R M) and non rigid (DFT N RM) molecules for the corresponding structures and energies. For the DFT analysis, the PBE exchange correlation functional and the large basis set A-PVTZ have been used. All structures and their respective energies calculated through the GA method, DFT R M and DFT N RM are compared and discussed. The proposed methodology showed to be very efficient in order to have quasi accurate global minima on the level of ab initio calculations and the data are discussed in the light of previously published results with particular attention to ((H 2 O) n (2 ≤ n ≤ 13)) clusters. The results suggest that the stabilization energy error for the empirical potentials used are additive with respect to the cluster size, roughly 0.5 kcal mol -1 per water molecule after ZPE correction. Finally, the approach of using GA/empirical potential structures as starting point for ab initio optimization methods showed to be a computationally manageable strategy to explore the potential energy surface of large systems at quantum level. In conclusion, this work proposes an alternative approach to accurately study properties of larger systems in a very efficient manner

  19. An approach based on genetic algorithms and DFT for studying clusters: (H{sub 2}O) {sub n} (2 {<=} n {<=} 13) cluster analysis

    Energy Technology Data Exchange (ETDEWEB)

    Sabato de Abreu e Silva, Elcio [Departamento de Quimica - ICEx, Universidade Federal de Minas Gerais, Av. Antonio Carlos 6627, Pampulha (31.270-901) Belo Horizonte, Minas Gerias (Brazil); Anderson Duarte, Helio [Departamento de Quimica - ICEx, Universidade Federal de Minas Gerais, Av. Antonio Carlos 6627, Pampulha (31.270-901) Belo Horizonte, Minas Gerias (Brazil); Belchior, Jadson Claudio [Departamento de Quimica - ICEx, Universidade Federal de Minas Gerais, Av. Antonio Carlos 6627, Pampulha (31.270-901) Belo Horizonte, Minas Gerias (Brazil)], E-mail: jadson@ufmg.br

    2006-04-21

    The present work proposes the application of a genetic algorithm (GA) for determining global minima to be used as seeds for a higher level ab initio method analysis such as density function theory (DFT). Water clusters ((H{sub 2}O) {sub n} (2 {<=} n {<=} 13)) are used as a test case and for the initial guesses four empirical potentials (TIP3P, TIP4P, TIP5P and ST2) were considered for the GA calculations. Two types of analysis were performed namely rigid (DFT{sub R}M) and non rigid (DFT{sub N}RM) molecules for the corresponding structures and energies. For the DFT analysis, the PBE exchange correlation functional and the large basis set A-PVTZ have been used. All structures and their respective energies calculated through the GA method, DFT{sub R}M and DFT{sub N}RM are compared and discussed. The proposed methodology showed to be very efficient in order to have quasi accurate global minima on the level of ab initio calculations and the data are discussed in the light of previously published results with particular attention to ((H{sub 2}O) {sub n} (2 {<=} n {<=} 13)) clusters. The results suggest that the stabilization energy error for the empirical potentials used are additive with respect to the cluster size, roughly 0.5 kcal mol{sup -1} per water molecule after ZPE correction. Finally, the approach of using GA/empirical potential structures as starting point for ab initio optimization methods showed to be a computationally manageable strategy to explore the potential energy surface of large systems at quantum level. In conclusion, this work proposes an alternative approach to accurately study properties of larger systems in a very efficient manner.

  20. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP...

  1. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Chen, Yin; El Eter, Mohamad; Chermak, Edrisse; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide

  2. On the site-specificity of polycarbonyl complexes in Cu/zeolites: combined experimental and DFT study

    Czech Academy of Sciences Publication Activity Database

    Bulánek, R.; Drobná, H.; Nachtigall, Petr; Rubeš, Miroslav; Bludský, Ota

    2006-01-01

    Roč. 8, č. 47 (2006), s. 5535-5542 ISSN 1463-9076 R&D Projects: GA MŠk(CZ) LC512; GA AV ČR(CZ) IAA400550613; GA ČR(CZ) GA203/06/0324 Institutional research plan: CEZ:AV0Z40550506 Keywords : vibrational dynamics * IR spectroscopy * periodic DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.892, year: 2006

  3. 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.

  4. 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.

  5. Finite-temperature orbital-free DFT molecular dynamics: Coupling PROFESS and QUANTUM ESPRESSO

    Science.gov (United States)

    Karasiev, Valentin V.; Sjostrom, Travis; Trickey, S. B.

    2014-12-01

    Implementation of orbital-free free-energy functionals in the PROFESS code and the coupling of PROFESS with the QUANTUM ESPRESSO code are described. The combination enables orbital-free DFT to drive ab initio molecular dynamics simulations on the same footing (algorithms, thermostats, convergence parameters, etc.) as for Kohn-Sham (KS) DFT. All the non-interacting free-energy functionals implemented are single-point: the local density approximation (LDA; also known as finite-T Thomas-Fermi, ftTF), the second-order gradient approximation (SGA or finite-T gradient-corrected TF), and our recently introduced finite-T generalized gradient approximations (ftGGA). Elimination of the KS orbital bottleneck via orbital-free methodology enables high-T simulations on ordinary computers, whereas those simulations would be costly or even prohibitively time-consuming for KS molecular dynamics (MD) on very high-performance computer systems. Example MD simulations on H over a temperature range 2000 K ≤ T ≤4,000,000 K are reported, with timings on small clusters (16-128 cores) and even laptops. With respect to KS-driven calculations, the orbital-free calculations are between a few times through a few hundreds of times faster.

  6. DFT study of IR and Raman spectra of phosphotrihydrazone dendrimer with terminal phenolic groups

    Science.gov (United States)

    Furer, V. L.; Vandyukov, A. E.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2017-09-01

    FT Raman and infrared spectra of phosphotrihydrazone (S)P[N(CH3)Ndbnd CHsbnd C6H4sbnd OH]3 (G0) were recorded. This compound is a zero generation phosphorus dendrimer with terminal phenolic groups. Optimal geometry and vibrational frequencies were calculated for G0 using the density functional theory (DFT). The molecule studied has C3 symmetry. In the molecule G0, each sbnd C6H4sbnd CHdbnd Nsbnd N(CH3)sbnd P arm is flat. Optimized geometric parameters correspond to experimental data. The core of the dendrimer manifests itself as a band at 647 cm-1 in the Raman spectrum of G0 related to Pdbnd S stretching. Phenolic end functions exhibit a well-defined band at 3374 cm-1 in the experimental IR spectrum of G0. The observed frequency of the OH stretching vibrations of the phenolic groups is lower than the theoretical value due to the intermolecular Osbnd H⋯O hydrogen bond. This hydrogen bond is also responsible for the higher intensity of this band in the experimental IR spectrum compared with the theoretical value. DFT calculations suggest full assignment of normal modes. Global and local descriptors characterize the reactivity of the core and end groups.

  7. Two and Three-Dimensional Nonlocal DFT for Inhomogeneous Fluids I: Algorithms and Parallelization

    Energy Technology Data Exchange (ETDEWEB)

    Frink, Laura J. Douglas; Salinger, Andrew

    1999-08-09

    Fluids adsorbed near surfaces, macromolecules, and in porous materials are inhomogeneous, inhibiting spatially varying density distributions. This inhomogeneity in the fluid plays an important role in controlling a wide variety of complex physical phenomena including wetting, self-assembly, corrosion, and molecular recognition. One of the key methods for studying the properties of inhomogeneous fluids in simple geometries has been density functional theory (DFT). However, there has been a conspicuous lack of calculations in complex 2D and 3D geometries. The computational difficulty arises from the need to perform nested integrals that are due to nonlocal terms in the free energy functional These integral equations are expensive both in evaluation time and in memory requirements; however, the expense can be mitigated by intelligent algorithms and the use of parallel computers. This paper details our efforts to develop efficient numerical algorithms so that no local DFT calculations in complex geometries that require two or three dimensions can be performed. The success of this implementation will enable the study of solvation effects at heterogeneous surfaces, in zeolites, in solvated (bio)polymers, and in colloidal suspensions.

  8. First-principles calculations on double-walled inorganic nanotubes with hexagonal chiralities

    International Nuclear Information System (INIS)

    Zhukovskii, Yuri F; Evarestov, Robert A; Bandura, Andrei V; Losev, Maxim V

    2011-01-01

    The two sets of commensurate double-walled boron nitride and titania hexagonally-structured nanotubes (DW BN and TiO 2 NTs) possessing either armchair- or zigzag-type chiralities have been considered, i.e., (n 1 ,n 1 )-(n 2 ,n 2 ) or (n 1 ,0)-(n 2 ,0), respectively. For symmetry analysis of these nanotubes, the line symmetry groups for one-periodic (1D) nanostructures with rotohelical symmetry have been applied. To analyze the structural and electronic properties of hexagonal DW NTs, a series of large-scale ab initio DFT-LCAO calculations have been performed using the hybrid Hartree-Fock/Kohn-Sham exchange-correlation functional PBE0 (as implemented in CRYSTAL-09 code). To establish the optimal inter-shell distances within DW NTs corresponding to the minima of calculated total energy, the chiral indices n 1 and n 2 of the constituent single-walled (SW) nanotubes have been successively varied.

  9. Predictions of Physicochemical Properties of Ionic Liquids with DFT

    Directory of Open Access Journals (Sweden)

    Karl Karu

    2016-07-01

    Full Text Available Nowadays, density functional theory (DFT-based high-throughput computational approach is becoming more efficient and, thus, attractive for finding advanced materials for electrochemical applications. In this work, we illustrate how theoretical models, computational methods, and informatics techniques can be put together to form a simple DFT-based throughput computational workflow for predicting physicochemical properties of room-temperature ionic liquids. The developed workflow has been used for screening a set of 48 ionic pairs and for analyzing the gathered data. The predicted relative electrochemical stabilities, ionic charges and dynamic properties of the investigated ionic liquids are discussed in the light of their potential practical applications.

  10. Are both symmetric and buckled dimers on Si(100) minima? Density functional and multireference perturbation theory calculations

    International Nuclear Information System (INIS)

    Jung, Yousung; Shao, Yihan; Gordon, Mark S.; Doren, Douglas J.; Head-Gordon, Martin

    2003-01-01

    We report a spin-unrestricted density functional theory (DFT) solution at the symmetric dimer structure for cluster models of Si(100). With this solution, it is shown that the symmetric structure is a minimum on the DFT potential energy surface, although higher in energy than the buckled structure. In restricted DFT calculations the symmetric structure is a saddle point connecting the two buckled minima. To further assess the effects of electron correlation on the relative energies of symmetric versus buckled dimers on Si(100), multireference second order perturbation theory (MRMP2) calculations are performed on these DFT optimized minima. The symmetric structure is predicted to be lower in energy than the buckled structure via MRMP2, while the reverse order is found by DFT. The implications for recent experimental interpretations are discussed

  11. 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.

  12. Overpotential for CO2 electroreduction lowered on strained penta-twinned Cu nanowires† †Electronic supplementary information (ESI) available: Details of DFT and MD calculations, CHE model and reaction pathways for C2H4 production. See DOI: 10.1039/c5sc02667a Click here for additional data file.

    Science.gov (United States)

    Chen, Zhengzheng; Zhang, Xu

    2015-01-01

    Based on first-principles calculations, we predict that penta-twinned Cu nanowires (NWs) are superior to conventional Cu catalysts for CO2 electroreduction. The penta-twinned NWs possess a combination of ultrahigh mechanical strength, large surface-to-volume ratios and an abundance of undercoordinated adsorption sites, all desirable for CO2 electroreduction. In particular, we show that the penta-twinned Cu NWs can withstand elastic strains orders of magnitude higher than their conventional counterpart, and as a result their CO2 electroreduction activities can be significantly enhanced by elastic tensile strains. With a moderate tensile strain, the bias potential for methane production at a decent current density (2 mA cm–2) can be reduced by 50%. On the other hand, the competing hydrogen evolution reaction can be suppressed by the tensile strains. The presence of H at the NW surface is found to have a minor effect on CO2 electroreduction. Finally, we propose to use graphene as a substrate to stretch deposited Cu NWs. PMID:28757974

  13. Prototropic tautomerism of 4-Methyl 1,2,4-Triazole-3-Thione molecule in solvent water medium: DFT and Car–Parrinello molecular dynamics study

    International Nuclear Information System (INIS)

    Dutta, Bipan; De, Rina; Chowdhury, Joydeep

    2015-01-01

    Highlights: • The tautomerism of 4-MTTN molecule in solvent water medium has been investigated. • CPMD presage the possibility of PT reactions through the solvent water medium. • Concerted PT processes in 4-MTTN have been estimated from the DFT and NBO analyses. • Percentage evolution and breaking of the concerned bonds are estimated. - Abstract: The ground state prototropic tautomerism of 4-Methyl 1,2,4-Triazole-3-Thione molecule in solvent water medium has been investigated with the aid of DFT and Car–Parrinello molecular dynamics (CPMD) simulation studies. The CPMD simulations envisage the possibility of proton transfer reactions of the molecule through the solvent water medium. Probable proton transfer pathways have been predicted from the DFT calculations which are substantiated by the natural bond orbital analyses. The evolution and breaking of the concerned bonds of the molecule for different proton transfer reaction pathways are also estimated.

  14. Efficient pseudospectral methods for density functional calculations

    International Nuclear Information System (INIS)

    Murphy, R. B.; Cao, Y.; Beachy, M. D.; Ringnalda, M. N.; Friesner, R. A.

    2000-01-01

    Novel improvements of the pseudospectral method for assembling the Coulomb operator are discussed. These improvements consist of a fast atom centered multipole method and a variation of the Head-Gordan J-engine analytic integral evaluation. The details of the methodology are discussed and performance evaluations presented for larger molecules within the context of DFT energy and gradient calculations. (c) 2000 American Institute of Physics

  15. 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.

  16. Quantitative structure-activity relationships of the antimalarial agent artemisinin and some of its derivatives - a DFT approach.

    Science.gov (United States)

    Rajkhowa, Sanchaita; Hussain, Iftikar; Hazarika, Kalyan K; Sarmah, Pubalee; Deka, Ramesh Chandra

    2013-09-01

    Artemisinin form the most important class of antimalarial agents currently available, and is a unique sesquiterpene peroxide occurring as a constituent of Artemisia annua. Artemisinin is effectively used in the treatment of drug-resistant Plasmodium falciparum and because of its rapid clearance of cerebral malaria, many clinically useful semisynthetic drugs for severe and complicated malaria have been developed. However, one of the major disadvantages of using artemisinins is their poor solubility either in oil or water and therefore, in order to overcome this difficulty many derivatives of artemisinin were prepared. A comparative study on the chemical reactivity of artemisinin and some of its derivatives is performed using density functional theory (DFT) calculations. DFT based global and local reactivity descriptors, such as hardness, chemical potential, electrophilicity index, Fukui function, and local philicity calculated at the optimized geometries are used to investigate the usefulness of these descriptors for understanding the reactive nature and reactive sites of the molecules. Multiple regression analysis is applied to build up a quantitative structure-activity relationship (QSAR) model based on the DFT based descriptors against the chloroquine-resistant, mefloquine-sensitive Plasmodium falciparum W-2 clone.

  17. 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.

  18. 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.

  19. 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.

  20. Electronic structure and equation of state of Sm2Co17 from first-principles DFT+ U

    Science.gov (United States)

    Huang, Patrick; Butch, Nicholas P.; Jeffries, Jason R.; McCall, Scott K.

    2013-03-01

    Rare-earth intermetallics have important applications as permanent magnet materials, and the rational optimization of their properties would benefit greatly from guidance from ab initio modeling. However, these systems are particularly challenging for current electronic structure methods. Here, we present an ab initio study of the prototype material Sm2Co17 and related compounds, using density functional theory with a Hubbard correction for the Sm 4 f-electrons (DFT+ U method) and ultrasoft pseudopotentials. The Hubbard U parameter is derived from first principles [Cococcioni and de Gironcoli, PRB 71, 035105 (2005)], not fit to experiment. Our calculations are in good agreement with recent photoemission measurements at ambient pressure and the equation of state up to 40 GPa, thus supporting the validity of our DFT+ U model. Prepared by LLNL under Contract DE-AC52-07NA27344.

  1. PdCu alloy nanoparticle-decorated copper nanotubes as enhanced electrocatalysts: DFT prediction validated by experiment

    Science.gov (United States)

    Wu, Dengfeng; Xu, Haoxiang; Cao, Dapeng; Fisher, Adrian; Gao, Yi; Cheng, Daojian

    2016-12-01

    In order to combine the advantages of both 0D and 1D nanostructured materials into a single catalyst, density functional theory (DFT) calculations have been used to study the PdCu alloy NP-decorated Cu nanotubes (PdCu@CuNTs). These present a significant improvement of the electrocatalytic activity of formic acid oxidation (FAO). Motivated by our theoretical work, we adopted the seed-mediated growth method to successfully synthesize the nanostructured PdCu@CuNTs. The new catalysts triple the catalytic activity for FAO, compared with commercial Pd/C. In summary, our work provides a new strategy for the DFT prediction and experimental synthesis of novel metal NP-decorated 1D nanostructures as electrocatalysts for fuel cells.

  2. 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)

  3. 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.

  4. A polarizable embedding DFT study of one-photon absorption in fluorescent proteins

    DEFF Research Database (Denmark)

    Beerepoot, Maarten; Steindal, Arnfinn H.; Kongsted, Jacob

    2013-01-01

    mutants (BFP, eGFP, YFP and eCFP). The observed trends in excitation energies among the FPs are reproduced by our approach when performing calculations directly on the crystal structures or when using structures extracted from a molecular dynamics simulations. However, in the former case, QM/MM geometry......A theoretical study of the one-photon absorption of five fluorescent proteins (FPs) is presented. The absorption properties are calculated using a polarizable embedding approach combined with density functional theory (PE-DFT) on the wild-type green fluorescent protein (wtGFP) and several of its...... optimization of the chromophores within a frozen protein environment is needed in order to reproduce the experimental trends. Explicit account of polarization in the force field is not needed to yield the correct trend between the different FPs, but is necessary for reproducing the experimentally observed red...

  5. Role of the lattice dynamics in La2-xBaxCuO4 superconductor based on DFT method

    Directory of Open Access Journals (Sweden)

    A Tavana

    2010-09-01

    Full Text Available Electron-phonon coupling parameters are calculated for La2-x BaxCuO4 cuprate superconductor in a wide range of dopings, from undoped to overdoped compounds. In this study we aim to study the quality of such calculations based on DFT method so, the results of σ GGA+U electronic structure calculations are also investigated. The obtained value for electron-phonon coupling is in the same order of previous calculations but, the value obtained for the Hubbard U parameter shows that, such methods are poor in the estimation of electronic correlations to decide about the role of phonons in these compounds based on their results. Moreover, existence of several structural phase transitions with temperature and doping, lead to larger error in these calculations. Based on the calculated phonon dispersions, structural phase transitions can be resulted which shows the ability of DFT in the study of structural properties and the weakness of the strongly correlations in this properties.

  6. DFT reactivity indices in confined many-electron atoms + ∫

    Indian Academy of Sciences (India)

    Unknown

    Functional Theory (DFT) based global descriptors of chemical reactivity for atoms .... interesting due to its utility as a model in the wide variety of applications ... hydrogen atom at Rc = 2⋅0 au is expected to correspond to the energy value of ...

  7. CHANNEL ESTIMATION FOR ZT DFT-s-OFDM

    DEFF Research Database (Denmark)

    2018-01-01

    A signal modulated according to zero-tail discrete Fourier transform spread orthogonal frequency division multiplexing (ZT DFT-s-OFDM) is received over a channel. The signal is down-sampled into a first sequence comprising N samples, N corresponding to the number of used subcarriers. The first Nh...

  8. DFT computations of the lattice constant, stable atomic structure and ...

    African Journals Online (AJOL)

    This paper presents the most stable atomic structure and lattice constant of Fullerenes (C60). FHI-aims DFT code was used to predict the stable structure and the computational lattice constant of C60. These were compared with known experimental structures and lattice constants of C60. The results obtained showed that ...

  9. Novel MC/BZY Proton Conductor: Materials Development, Device Evaluation, and Theoretical Exploration using CI and DFT Methods

    Science.gov (United States)

    2017-09-05

    the protons produced by surface defect reactions were transferred to the neighboring carbonate-ions ( CO3 2-) at the BZY/MC interface to form HCO3...static DFT study of the proton transfer in the crystal structure of lithium carbonate 33. The calculated energy barrier was 0.34 eV along the...However, the value is only 20.5 kcal/mol in Ref. 33, which was calculated based on a single molecule of HCO3 -. To eliminate possible uncertainty in the

  10. 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.

  11. DFT and experimental studies on structure and spectroscopic parameters of 3,6-diiodo-9-ethyl-9H-carbazole

    DEFF Research Database (Denmark)

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

    2016-01-01

    The first report on crystal and molecular structure of 3,6-diiodo-9-ethyl-9H-carbazole is presented. Experimental room-temperature X-ray and 13C chemical shift studies were supported by advanced theoretical calculations using density functional theory (DFT). The 13C nuclear magnetic shieldings were...... predicted at the non-relativistic and relativistic level of theory using the zeroth-order regular approximation (ZORA). Theoretical relativistic calculations of chemical shifts of carbons C3 and C6, directly bonded to iodine atoms, produced a reasonable agreement with experiment (initial deviation from...

  12. Direct Production of Propene from the Thermolysis of Poly(β-hydroxybutyrate) (PHB). An Experimental and DFT Investigation.

    Science.gov (United States)

    Clark, Jared M; Pilath, Heidi M; Mittal, Ashutosh; Michener, William E; Robichaud, David J; Johnson, David K

    2016-01-28

    We demonstrate a synthetic route toward the production of propene directly from poly(β-hydroxybutyrate) (PHB), the most common of a wide range of high-molecular-mass microbial polyhydroxyalkanoates. Propene, a major commercial hydrocarbon, was obtained from the depolymerization of PHB and subsequent decarboxylation of the crotonic acid monomer in good yields (up to 75 mol %). The energetics of PHB depolymerization and the gas-phase decarboxylation of crotonic acid were also studied using density functional theory (DFT). The average activation energy for the cleavage of the R'C(O)O-R linkage is calculated to be 163.9 ± 7.0 kJ mol(-1). Intramolecular, autoacceleration effects regarding the depolymerization of PHB, as suggested in some literature accounts, arising from the formation of crotonyl and carboxyl functional groups in the products could not be confirmed by the results of DFT and microkinetic modeling. DFT results, however, suggest that intermolecular catalysis involving terminal carboxyl groups may accelerate PHB depolymerization. Activation energies for this process were estimated to be about 20 kJ mol(-1) lower than that for the noncatalyzed ester cleavage, 144.3 ± 6.4 kJ mol(-1). DFT calculations predict the decarboxylation of crotonic acid to follow second-order kinetics with an activation energy of 147.5 ± 6.3 kJ mol(-1), consistent with that measured experimentally, 146.9 kJ mol(-1). Microkinetic modeling of the PHB to propene overall reaction predicts decarboxylation of crotonic acid to be the rate-limiting step, consistent with experimental observations. The results also indicate that improvements made to enhance the isomerization of crotonic acid to vinylacetic acid will improve the direct conversion of PHB to propene.

  13. Structural studies on Mannich bases of 2-Hydroxy-3,4,5,6-tetrachlorobenzene. An UV, IR, NMR and DFT study. A mini-review

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Spanget-Larsen, Jens

    2016-01-01

    Mannich bases of 2-Hydroxy-3,4,5,6-tetrachlorobenzene are chosen as an exemplary case for tautomeric Mannich bases. Molecular structures are calculated. OH stretching frequencies are rationalized based on DFT calculations. Intrinsic deuterium isotope effects on 13C chemical shifts in the M-form a......-form are estimated based on OH bond lengths. The observed deuterium isotope effects on 13C chemical shifts are demonstrated to be largely of equilibrium type except at ambient temperatures....

  14. Study on the interactions of Ag nanoparticles with low molecular weight organic matter using first principles calculations

    CSIR Research Space (South Africa)

    Nyangiwe, Nangamso N

    2017-10-01

    Full Text Available with natural organic matter (NOMs) and ENPs inherent physicochemical properties. Herein, density functional theory (DFT), classical lattice dynamics (CLD), and quantum mechanical calculations based on frontier molecular orbital (FMO) theory were applied...

  15. Synthesis, characterization, spectroscopic properties and DFT study of a new pyridazinone family

    Science.gov (United States)

    Arrue, Lily; Rey, Marina; Rubilar-Hernandez, Carlos; Correa, Sebastian; Molins, Elies; Norambuena, Lorena; Zarate, Ximena; Schott, Eduardo

    2017-11-01

    Nitrogen compounds are widely investigated due to their pharmacological properties such as antihypertensive, antinociceptive, antibacterial, antifungal, analgesic, anticancer and inhibition activities and lately even as pesticide. In this context, we present the synthesis of new compounds: (E)-6-(3,4-dimethoxyphenyl)-3-(3-(3,4-dimethoxyphenyl)acryloyl)-1-(4-R-phenyl)- 5,6-dihydropyridazin-4(1H)-one (with R = sbnd H(1), -Cl(2), -Br(3), sbnd I(4) and sbnd COOH(5)) that was carried out by reaction of (1E, 6E)-1,7-bis(3,4-dimethoxyphenyl)hepta-1,6-diene-3,5-dione with a substituted phenylamine with general formula p-R-C6H4sbnd NH2 (R = sbnd H (1), sbnd Cl (2), -Br(3), sbnd I(4) and sbnd COOH(5)). This is the first synthesis report of a pyridazinone using as precursors a curcuminoid derivative and a diazonium salt formed in situ. All compounds were characterized by EA, FT-IR, UV-Vis, Emission,1H- and13C-NMR spectroscopy and the crystalline and molecular structure of 4 was solved by X-rays diffraction method. DFT and TD-DFT quantum chemical calculations were also employed to characterize the compounds and provide a rational explanation to the spectroscopic properties. To assess the biological activity of the systems, we focused on pesticide tests on compound 2, which showed an inhibitory effect in plant growth of Agrostis tenuis Higland.

  16. 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.

  17. Flux formulation of DFT on group manifolds and generalized Scherk-Schwarz compactifications

    Energy Technology Data Exchange (ETDEWEB)

    Bosque, Pascal du [Max-Planck-Institut für Physik,Föhringer Ring 6, 80805 München (Germany); Arnold-Sommerfeld-Center für Theoretische Physik,Fakultät für Physik, Ludwig-Maximilians-Universität München,Theresienstraße 37, 80333 München (Germany); Hassler, Falk [University of North Carolina, Department of Physics and Astronomy,Phillips Hall, CB #3255, 120 E. Cameron Ave., Chapel Hill, NC 27599-3255 (United States); City University of New York, The Graduate Center,365 Fifth Avenue, New York, NY 10016 (United States); Columbia University, Department of Physics,Pupin Hall, 550 West 120th St., New York, NY 10027 (United States); Lüst, Dieter [Max-Planck-Institut für Physik,Föhringer Ring 6, 80805 München (Germany); Arnold-Sommerfeld-Center für Theoretische Physik,Fakultät für Physik, Ludwig-Maximilians-Universität München,Theresienstraße 37, 80333 München (Germany)

    2016-02-04

    A flux formulation of Double Field Theory on group manifold is derived and applied to study generalized Scherk-Schwarz compactifications, which give rise to a bosonic subsector of half-maximal, electrically gauged supergravities. In contrast to the flux formulation of original DFT, the covariant fluxes split into a fluctuation and a background part. The latter is connected to a 2D-dimensional, pseudo Riemannian manifold, which is isomorphic to a Lie group embedded into O(D,D). All fields and parameters of generalized diffeomorphisms are supported on this manifold, whose metric is spanned by the background vielbein E{sub A}{sup I}∈ GL(2D). This vielbein takes the role of the twist in conventional generalized Scherk-Schwarz compactifications. By doing so, it solves the long standing problem of constructing an appropriate twist for each solution of the embedding tensor. Using the geometric structure, absent in original DFT, E{sub A}{sup I} is identified with the left invariant Maurer-Cartan form on the group manifold, in the same way as it is done in geometric Scherk-Schwarz reductions. We show in detail how the Maurer-Cartan form for semisimple and solvable Lie groups is constructed starting from the Lie algebra. For all compact embeddings in O(3,3), we calculate E{sub A}{sup I}.

  18. Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study

    Directory of Open Access Journals (Sweden)

    Giuseppe Mele

    2011-12-01

    Full Text Available Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.

  19. Synthesis, X-ray Structure, Spectroscopic Properties and DFT Studies of a Novel Schiff Base

    Directory of Open Access Journals (Sweden)

    Kew-Yu Chen

    2014-10-01

    Full Text Available A series of Schiff bases, salicylideneaniline derivatives 1–4, was synthesized under mild conditions and characterized by 1H NMR, HRMS, UV-Vis and fluorescence spectra, and single-crystal X-ray diffraction. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess an intramolecular six-membered-ring hydrogen bond. A weak intramolecular C–H×××F hydrogen bond is also observed in fluoro-functionalized Schiff base 4, which generates another S(6 ring motif. The C–H×××F hydrogen bond further stabilizes its structure and leads it to form a planar configuration. Compounds 1–3 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 4 shows remarkable dual emission originated from the excited-state intramolecular charge transfer (ESICT and excited-state intramolecular proton transfer (ESIPT states. Furthermore, the geometric structures, frontier molecular orbitals (MOs and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT and time-dependent DFT calculations.

  20. Probing the (110)-Oriented plane of rutile ZnF2: A DFT investigation

    Science.gov (United States)

    Tamijani, Ali Abbaspour; Ebrahimiaqda, Elham

    2017-12-01

    For many years, rutile-like crystals have given rise to pronounced enthusiasm amongst mineralogists. In this context, rutile-type ZnF2 has found numerous applications across a variety of disciplines, ranging from material sciences to optoelectronics. Surprisingly, very limited literature is concerned with the molecular adsorption on ZnF2 surfaces and related energetics. Additionally, surface probing with small particles is a well-entrenched technique to analyze the interfacial properties. In this regard, small organic species are valuable picks. In the present work, we have employed electronic structure calculations to simulate the adsorption of methane, chloroform, pyrrole, benzene, naphthalene, anthracene, tetracene and pentacene at the (110) plane of rutile ZnF2. Dispersion-corrected DFT method was chosen to predict the binding energies and structures of molecule-adsorbed surfaces. Interestingly, a linear proportionality relationship was found between the binding energies of aromatic adsorbates and their respective molecular lengths. By applying this relationship, we were able to predict the adsorption energy of pentacene on ZnF2 to within 2% of our DFT-based result.