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Sample records for dft based computational

  1. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-04-13

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

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

    Science.gov (United States)

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

    2018-05-01

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

  5. A DFT-Based Computational-Experimental Methodology for Synthetic Chemistry: Example of Application to the Catalytic Opening of Epoxides by Titanocene.

    Science.gov (United States)

    Jaraíz, Martín; Enríquez, Lourdes; Pinacho, Ruth; Rubio, José E; Lesarri, Alberto; López-Pérez, José L

    2017-04-07

    A novel DFT-based Reaction Kinetics (DFT-RK) simulation approach, employed in combination with real-time data from reaction monitoring instrumentation (like UV-vis, FTIR, Raman, and 2D NMR benchtop spectrometers), is shown to provide a detailed methodology for the analysis and design of complex synthetic chemistry schemes. As an example, it is applied to the opening of epoxides by titanocene in THF, a catalytic system with abundant experimental data available. Through a DFT-RK analysis of real-time IR data, we have developed a comprehensive mechanistic model that opens new perspectives to understand previous experiments. Although derived specifically from the opening of epoxides, the prediction capabilities of the model, built on elementary reactions, together with its practical side (reaction kinetics simulations of real experimental conditions) make it a useful simulation tool for the design of new experiments, as well as for the conception and development of improved versions of the reagents. From the perspective of the methodology employed, because both the computational (DFT-RK) and the experimental (spectroscopic data) components can follow the time evolution of several species simultaneously, it is expected to provide a helpful tool for the study of complex systems in synthetic chemistry.

  6. 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.

  7. 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.

  8. 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

  9. 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 ...

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Computer-Aided Test Flow in Core-Based Design

    NARCIS (Netherlands)

    Zivkovic, V.; Tangelder, R.J.W.T.; Kerkhoff, Hans G.

    2000-01-01

    This paper copes with the efficient test-pattern generation in a core-based design. A consistent Computer-Aided Test (CAT) flow is proposed based on the required core-test strategy. It generates a test-pattern set for the embedded cores with high fault coverage and low DfT area overhead. The CAT

  15. Spectroscopic characterization, antimicrobial activity, DFT computation and docking studies of sulfonamide Schiff bases

    Science.gov (United States)

    Mondal, Sudipa; Mandal, Santi M.; Mondal, Tapan Kumar; Sinha, Chittaranjan

    2017-01-01

    Schiff bases synthesised from the condensation of 2-(hydroxy)naphthaldehyde and sulfonamides (sufathiazole (STZ), sulfapyridine (SPY), sulfadiazine (SDZ), sulfamerazine (SMZ) and sulfaguanidine (SGN)) are characterized by different spectroscopic data (FTIR, UV-Vis, Mass, NMR) and two of them, (E)-4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-N-(thiazol-2-yl)benzenesulfonamide (1a) and (E)-N-(diaminomethylene)-4-(((2-hydroxynaphthalen-1-yl)methylene)amino)benzenesulfonamide (1e) have been confirmed by single crystal X-ray structure determination. Antimicrobial activities of the Schiff bases have been evaluated against certified and resistant Gram positive (Staphylococcus aureus, Enterococcus facelis) and Gram negative (Streptococcus pyogenes, Salmonella typhi, Shigella dysenteriae, Shigella flexneri, Klebsiella pneumonia) pathogens. Performance of Schiff base against the resistant pathogens are better than standard stain and MIC data lie 32-128 μg/ml while parent sulfonamides are effectively inactive (MIC >512 μg/ml). The DFT optimized structures of the Schiff bases have been used to accomplish molecular docking studies with DHPS (dihydropteroate synthase) protein structure (downloaded from Protein Data Bank) to establish the most preferred mode of interaction. ADMET filtration, Cytotoxicity (MTT assay) and haemolysis assay have been examined for evaluation of druglike character.

  16. 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.

  17. 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)

  18. Synthesis of novel styryl derivatives from 4-chloro-2-(morpholin-4-yl)-1,3-thiazole-5-carbaldehyde, study of their photophysical properties and TD-DFT computations

    International Nuclear Information System (INIS)

    Sekar, Nagaiyan; Umape, Prashant G.; Padalkar, Vikas S.; Tayade, Rajratna P.; Ramasami, Ponnadurai

    2014-01-01

    Novel fluorescent styryl push–pull compounds having electron donating thiazole unit were synthesized by condensing 4-chloro-2-(morpholin-4-yl)-1,3-thiazole-5-carbaldehyde with active methylene compounds via classical Knoevenagel condensation. The synthesized styryl molecules were characterized by spectral analysis. Photophysical properties of these styryl derivatives were analyzed and the effect of change in solvent polarity and viscosity on their absorptive and emissive properties has been investigated. Density functional theory (DFT) and time dependent-density functional theory (TD-DFT) computations have been used to understand the structural, molecular, electronic and photophysical parameters of push–pull dyes. Bakhshiev and Kawski–Chamma–Viallet correlations were used to calculate the ratio of ground to excited state dipole moment of the synthesized novel styryl compounds. -- Highlights: •Novel styryl derivatives are synthesized from thiazole aldehyde. •Photophysical properties of styryl derivatives were evaluated and supported by TD-DFT computations. •Experimental photophysical results are in good agreement with the theoretical results obtained by TD-DFT computations. •Compounds show fluorescence in solid state as well as in solvents of different polarities

  19. 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.

  20. An EQT-based cDFT approach for a confined Lennard-Jones fluid mixture

    Energy Technology Data Exchange (ETDEWEB)

    Motevaselian, M. H.; Mashayak, S. Y.; Aluru, N. R., E-mail: aluru@illinois.edu [Department of Mechanical Science and Engineering, Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States)

    2015-09-28

    Empirical potential-based quasi-continuum theory (EQT) provides a route to incorporate atomistic detail into continuum framework such as the Nernst-Planck equation. EQT can also be used to construct a grand potential functional for classical density functional theory (cDFT). The combination of EQT and cDFT provides a simple and fast approach to predict the inhomogeneous density, potential profiles, and thermodynamic properties of confined fluids. We extend the EQT-cDFT approach to confined fluid mixtures and demonstrate it by simulating a mixture of methane and hydrogen inside slit-like channels of graphene. We show that the EQT-cDFT predictions for the structure of the confined fluid mixture compare well with the molecular dynamics simulation results. In addition, our results show that graphene slit nanopores exhibit a selective adsorption of methane over hydrogen.

  1. DFT-based offset-QAM OFDM for optical communications.

    Science.gov (United States)

    Zhao, Jian

    2014-01-13

    We experimentally demonstrate and numerically investigate a discrete-Fourier-transform (DFT) based offset quadrature-amplitude-modulation (offset-QAM) orthogonal frequency division multiplexing (OFDM) system. We investigate the scheme using a set of square-root-raised-cosine functions and a set of super-Gaussian functions as signal spectra. It is shown that offset-QAM OFDM exhibits negligible penalty for all investigated spectra, in contrast to rectangular-function based Nyquist FDM (N-FDM) and sinc-function based conventional OFDM (C-OFDM). The required guard interval (GI) length for dispersion compensation in offset-QAM OFDM is analyzed and shown to scale with twice the subcarrier spacing rather than the full OFDM bandwidth. Experimental results show that 38-Gb/s offset-16QAM OFDM supports 600-km fiber transmission with negligible penalty in the absence of GI while a GI length of eight is required in C-OFDM. Further numerical simulations show that by avoiding the GI, 112-Gb/s polarization multiplexed offset-4QAM OFDM can achieve 23% increase in net data rate over C-OFDM under the same transmission reach. We also discuss the design of the pulse-shaping filter in the DFT-based implementation and show that when compared to N-FDM, the required memory length of the filter for pulse shaping can be reduced from 60 to 2 in offset-QAM OFDM regardless of the fiber length.

  2. A comparison of different discrimination parameters for the DFT-based PSD method in fast scintillators

    International Nuclear Information System (INIS)

    Liu, G.; Yang, J.; Luo, X.L.; Lin, C.B.; Peng, J.X.; Yang, Y.

    2013-01-01

    Although the discrete Fourier transform (DFT) based pulse shape discrimination (PSD) method, realized by transforming the digitized scintillation pulses into frequency coefficients by using DFT, has been proven to effectively discriminate neutrons and γ rays, its discrimination performance depends strongly on the selection of the discrimination parameter obtained by the combination of these frequency coefficients. In order to thoroughly understand and apply the DFT-based PSD in organic scintillation detectors, a comparison of three different discrimination parameters, i.e. the amplitude of zero-frequency component, the amplitude difference between the amplitude of zero-frequency component and the amplitude of base-frequency component, and the ratio of the amplitude of base-frequency component to the amplitude of zero-frequency component, is described in this paper. An experimental setup consisting of an Americium–Beryllium (Am–Be) source, a BC501A liquid scintillator detector, and a 5Gsample/s 8-bit oscilloscope was built to assess the performance of the DFT-based PSD with each of these discrimination parameters in terms of the figure-of-merit (based on the separation of the event distributions). The third technique, which uses the ratio of the amplitude of base-frequency component to the amplitude of zero-frequency component as the discrimination parameter, is observed to provide the best discrimination performance in this research. - Highlights: • The spectrum difference between neutron pulse and γ-ray pulse was investigated. • The DFT-based PSD with different parameter definitions was assessed. • The way of using the ratio of magnitude spectrum provides the best performance. • The performance differences were explained from noise suppression features

  3. 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.

  4. 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

  5. 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

  6. Channel estimation in DFT-based offset-QAM OFDM systems.

    Science.gov (United States)

    Zhao, Jian

    2014-10-20

    Offset quadrature amplitude modulation (offset-QAM) orthogonal frequency division multiplexing (OFDM) exhibits enhanced net data rates compared to conventional OFDM, and reduced complexity compared to Nyquist FDM (N-FDM). However, channel estimation in discrete-Fourier-transform (DFT) based offset-QAM OFDM is different from that in conventional OFDM and requires particular study. In this paper, we derive a closed-form expression for the demultiplexed signal in DFT-based offset-QAM systems and show that although the residual crosstalk is orthogonal to the decoded signal, its existence degrades the channel estimation performance when the conventional least-square method is applied. We propose and investigate four channel estimation algorithms for offset-QAM OFDM that vary in terms of performance, complexity, and tolerance to system parameters. It is theoretically and experimentally shown that simple channel estimation can be realized in offset-QAM OFDM with the achieved performance close to the theoretical limit. This, together with the existing advantages over conventional OFDM and N-FDM, makes this technology very promising for optical communication systems.

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

    Directory of Open Access Journals (Sweden)

    Jumaidil Awal

    2016-01-01

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

  8. 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.

  9. Experimental demonstration of OFDM/OQAM transmission with DFT-based channel estimation for visible laser light communications

    Science.gov (United States)

    He, Jing; Shi, Jin; Deng, Rui; Chen, Lin

    2017-08-01

    Recently, visible light communication (VLC) based on light-emitting diodes (LEDs) is considered as a candidate technology for fifth-generation (5G) communications, VLC is free of electromagnetic interference and it can simplify the integration of VLC into heterogeneous wireless networks. Due to the data rates of VLC system limited by the low pumping efficiency, small output power and narrow modulation bandwidth, visible laser light communication (VLLC) system with laser diode (LD) has paid more attention. In addition, orthogonal frequency division multiplexing/offset quadrature amplitude modulation (OFDM/OQAM) is currently attracting attention in optical communications. Due to the non-requirement of cyclic prefix (CP) and time-frequency domain well-localized pulse shapes, it can achieve high spectral efficiency. Moreover, OFDM/OQAM has lower out-of-band power leakage so that it increases the system robustness against inter-carrier interference (ICI) and frequency offset. In this paper, a Discrete Fourier Transform (DFT)-based channel estimation scheme combined with the interference approximation method (IAM) is proposed and experimentally demonstrated for VLLC OFDM/OQAM system. The performance of VLLC OFDM/OQAM system with and without DFT-based channel estimation is investigated. Moreover, the proposed DFT-based channel estimation scheme and the intra-symbol frequency-domain averaging (ISFA)-based method are also compared for the VLLC OFDM/OQAM system. The experimental results show that, the performance of EVM using the DFT-based channel estimation scheme is improved about 3dB compared with the conventional IAM method. In addition, the DFT-based channel estimation scheme can resist the channel noise effectively than that of the ISFA-based method.

  10. A DFT-based genetic algorithm search for AuCu nanoalloy electrocatalysts for CO2 reduction

    DEFF Research Database (Denmark)

    Lysgaard, Steen; Mýrdal, Jón Steinar Garðarsson; Hansen, Heine Anton

    2015-01-01

    Using a DFT-based genetic algorithm (GA) approach, we have determined the most stable structure and stoichiometry of a 309-atom icosahedral AuCu nanoalloy, for potential use as an electrocatalyst for CO2 reduction. The identified core–shell nano-particle consists of a copper core interspersed....... This shows that the mixed Cu135@Au174 core–shell nanoalloy has a similar adsorption energy, for the most favorable site, as a pure gold nano-particle. Cu, however, has the effect of stabilizing the icosahedral structure because Au particles are easily distorted when adding adsorbates....... that it is possible to use the LCAO mode to obtain a realistic estimate of the molecular chemisorption energy for systems where the computation in normal grid mode is not computationally feasible. These corrections are employed when calculating adsorption energies on the Cu, Au and most stable mixed particles...

  11. 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.

  12. Electromechanical and Chemical Sensing at the Nanoscale: DFT and Transport Modeling

    Science.gov (United States)

    Maiti, Amitesh

    Of the many nanoelectronic applications proposed for near to medium-term commercial deployment, sensors based on carbon nanotubes (CNT) and metal-oxide nanowires are receiving significant attention from researchers. Such devices typically operate on the basis of the changes of electrical response characteristics of the active component (CNT or nanowire) when subjected to an externally applied mechanical stress or the adsorption of a chemical or bio-molecule. Practical development of such technologies can greatly benefit from quantum chemical modeling based on density functional theory (DFT), and from electronic transport modeling based on non-equilibrium Green's function (NEGF). DFT can compute useful quantities like possible bond-rearrangements, binding energy, charge transfer, and changes to the electronic structure, while NEGF can predict changes in electronic transport behavior and contact resistance. Effects of surrounding medium and intrinsic structural defects can also be taken into account. In this work we review some recent DFT and transport investigations on (1) CNT-based nano-electromechanical sensors (NEMS) and (2) gas-sensing properties of CNTs and metal-oxide nanowires. We also briefly discuss our current understanding of CNT-metal contacts which, depending upon the metal, the deposition technique, and the masking method can have a significant effect on device performance.

  13. DFT based spatial multiplexing and maximum ratio transmission for mm-wawe large MIMO

    DEFF Research Database (Denmark)

    Phan-Huy, D.-T.; Tölli, A.; Rajatheva, N.

    2014-01-01

    -SM-MRT). When the DFT-SM scheme alone is used, the data streams are either mapped onto different angles of departures in the case of aligned linear arrays, or mapped onto different orbital angular momentums in the case of aligned circular arrays. Maximum ratio transmission pre-equalizes the channel......By using large point-to-point multiple input multiple output (MIMO), spatial multiplexing of a large number of data streams in wireless communications using millimeter-waves (mm-waves) can be achieved. However, according to the antenna spacing and transmitter-receiver distance, the MIMO channel...... is likely to be ill-conditioned. In such conditions, highly complex schemes such as the singular value decomposition (SVD) are necessary. In this paper, we propose a new low complexity system called discrete Fourier transform based spatial multiplexing (DFT-SM) with maximum ratio transmission (DFT...

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. Techniques for Computing the DFT Using the Residue Fermat Number Systems and VLSI

    Science.gov (United States)

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

    1985-01-01

    The integer complex multiplier and adder over the direct sum of two copies of a finite field is specialized to the direct sum of the rings of integers modulo Fermat numbers. Such multiplications and additions can be used in the implementation of a discrete Fourier transform (DFT) of a sequence of complex numbers. The advantage of the present approach is that the number of multiplications needed for the DFT can be reduced substantially over the previous approach. The architectural designs using this approach are regular, simple, expandable and, therefore, naturally suitable for VLSI implementation.

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

    Indian Academy of Sciences (India)

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

  2. 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.

  3. 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.

  4. A New Approach for Studying Bond Rupture/Closure of a Spiro Benzopyran Photochromic Material: Reactivity Descriptors Derived from Frontier Orbitals and DFT Computed Electrostatic Potential Energy Surface Maps

    Directory of Open Access Journals (Sweden)

    M. S. A. Abdel-Mottaleb

    2016-01-01

    Full Text Available This paper focuses on computations technique within the framework of the TD-DFT theory for studying the relationship between structure-properties of reversible conversion of photochromic materials. Specifically, we report on 1′,3′-dihydro-8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2′-(2H-indole] (SP and its isomers. TD-DFT calculated UV-Vis electronic spectra of the closed and open isomers of this photochromic material are in excellent agreement with the experimental results. Moreover, this paper reports on the results of theoretical investigations of reactivity indices that may govern the conversion between spiropyrans and its isomers. In addition, the solvent and rigidity of the medium significantly control the thermal bleaching of the photogenerated colored isomers and hence the switch ability pattern of the photochromic material. The effect of molecular structure computed by DFT in gas-phase and solvents on Cspiro-O bond length has been shown to correlate with photochromic properties. For this compound, DFT optimized geometry could be used to predict photochromism. Furthermore, in an attempt to predict the driving force for MC → SP, this work explores, for the first time, profitable exploitation of the calculated and visualized mapped electrostatic potential energy surfaces (ESP map. Interestingly, it seems that the electrostatic potential forces over the molecular fragments govern spirobond rupture/closure reactions. Thermodynamically, all-trans-colored isomer (CTT is the most stable merocyanine-like form.

  5. 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

  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. The qualitative and quantitative accuracy of DFT methods in computing 1J(C–F), 1J(C–N) and nJ(F–F) spin–spin coupling of fluorobenzene and fluoropyridine molecules

    International Nuclear Information System (INIS)

    Adeniyi, Adebayo A.; Ajibade, Peter A.

    2015-01-01

    The qualitative and quantitative quality of DFT methods combined with different basis sets in computing the J-coupling of the types 1 J(C–F) and n J(F–F) are investigated for the fluorobenzene and fluoropyridine derivatives. Interestingly, all of the computational methods perfectly reproduced the experimental order for n J(F–F) but many failed to reproduce the experimental order for 1 J(C–F) coupling. The functional PBEPBE gives the best quantitative values that are closer to the experimental spin–spin coupling when combined with the basis sets aug-cc-pVDZ and DGDZVP but is also part of the methods that fail to perfectly reproduce the experimental order for the 1 J(C–F) coupling. The basis set DGDZVP combined with all the methods except with PBEPBE perfectly reproduces the 1 J(C–F) experimental order. All the methods reproduce either the positive or the negative sign of the experimental spin–spin coupling except for the basis set 6-31+G(d,p) which fails to reproduce the experimental positive value of 3 J(F–F) regardless of what type of DFT methods was used. The values of the FC term is far higher than all other Ramsey terms in the one bond 1 J(C–F) coupling but in the two, three and four bonds n J(F–F) the values of PSO and SD are higher. - Graphical abstract: DFT methods were used to compute the J-coupling of molecules benf, benf2, benf2c, benf2c2, pyrf, pyrfc and pyrfc2, and are presented. Right combination of DFT functional with basis set can reproduce high level EOM-CCSD and experimental J-coupling results. All the methods can reproduce the qualitative order of the experimental J-coupling but not all reproduce the quantitative. The best quantitative results were obtained from PBEPBE combined with the high basis set aug-cc-pVDZ Also, PBEPBE combines with lower basis set DGDZVP to give a highly similar value. - Highlights: • DFT methods were used to compute the J-coupling of the molecules. • Right combination of DFT functional with basis

  8. 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

  9. 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.

  10. 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.

  11. Successes and failures of DFT functionals in acid/base and redox reactions of organic and biochemical interest

    OpenAIRE

    Silva, Pedro J.; Ramos, Maria João

    2011-01-01

    The performance of 18 different DFT functionals in the prediction of absolute and relative energies of organic and biochemical acid/base and redox reactions was evaluated, using MP2 extrapolated to the complete basis set limit and CCSD(T)/aug-cc-pVTZ energies as benchmark. Absolute reduction energies were predicted with relatively large average errors (2–4 kcal mol−1) except for the best functional, PBE0 (1.3 ± 1.2 kcal mol−1). The DFT predictions of relative reduction energies afforded mean ...

  12. 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 ...

  13. DFTBaby: A software package for non-adiabatic molecular dynamics simulations based on long-range corrected tight-binding TD-DFT(B)

    Science.gov (United States)

    Humeniuk, Alexander; Mitrić, Roland

    2017-12-01

    A software package, called DFTBaby, is published, which provides the electronic structure needed for running non-adiabatic molecular dynamics simulations at the level of tight-binding DFT. A long-range correction is incorporated to avoid spurious charge transfer states. Excited state energies, their analytic gradients and scalar non-adiabatic couplings are computed using tight-binding TD-DFT. These quantities are fed into a molecular dynamics code, which integrates Newton's equations of motion for the nuclei together with the electronic Schrödinger equation. Non-adiabatic effects are included by surface hopping. As an example, the program is applied to the optimization of excited states and non-adiabatic dynamics of polyfluorene. The python and Fortran source code is available at http://www.dftbaby.chemie.uni-wuerzburg.de.

  14. A projection-free method for representing plane-wave DFT results in an atom-centered basis

    International Nuclear Information System (INIS)

    Dunnington, Benjamin D.; Schmidt, J. R.

    2015-01-01

    Plane wave density functional theory (DFT) is a powerful tool for gaining accurate, atomic level insight into bulk and surface structures. Yet, the delocalized nature of the plane wave basis set hinders the application of many powerful post-computation analysis approaches, many of which rely on localized atom-centered basis sets. Traditionally, this gap has been bridged via projection-based techniques from a plane wave to atom-centered basis. We instead propose an alternative projection-free approach utilizing direct calculation of matrix elements of the converged plane wave DFT Hamiltonian in an atom-centered basis. This projection-free approach yields a number of compelling advantages, including strict orthonormality of the resulting bands without artificial band mixing and access to the Hamiltonian matrix elements, while faithfully preserving the underlying DFT band structure. The resulting atomic orbital representation of the Kohn-Sham wavefunction and Hamiltonian provides a gateway to a wide variety of analysis approaches. We demonstrate the utility of the approach for a diverse set of chemical systems and example analysis approaches

  15. Cyanidin-Based Novel Organic Sensitizer for Efficient Dye-Sensitized Solar Cells: DFT/TDDFT Study

    Directory of Open Access Journals (Sweden)

    Kalpana Galappaththi

    2017-01-01

    Full Text Available Cyanidin is widely considered as a potential natural sensitizer in dye-sensitized solar cells due to its promising electron-donating and electron-accepting abilities and cheap availability. We consider modifications of cyanidin structure in order to obtain broader UV-Vis absorption and hence to achieve better performance in DSSC. The modified molecule consists of cyanidin and the benzothiadiazolylbenzoic acid group, where the benzothiadiazolylbenzoic acid group is attached to the cyanidin molecule by replacing one hydroxyl group. The resulting structure was then computationally simulated by using the Spartan’10 software package. The molecular geometries, electronic structures, absorption spectra, and electron injections of the newly designed organic sensitizer were investigated in this work through density functional theory (DFT and time-dependent density functional theory (TDDFT calculations using the Gaussian’09W software package. Furthermore, TDDFT computational calculations were performed on cyanadin and benzothiadiazolylbenzoic acid separately, as reference. The computational studies on the new sensitizer have shown a reduced HOMO-LUMO gap; bathochromic and hyperchromic shifts of absorption spectra range up to near-infrared region revealing its enhanced ability to sensitize DSSCs.

  16. DFT study on the attacking mechanisms of H and OH radicals to G-C and A-T base pairs in water

    Energy Technology Data Exchange (ETDEWEB)

    Okutsu, N.; Shimamura, K.; Shimizu, E.; Kurita, N., E-mail: kurita@cs.tut.ac.jp [Department of Computer Science and Engineering, Toyohashi University of Technology, Toyohashi, Aichi, 441-8580 (Japan); Shulga, S. [Institute for Food Biotechnology and Genomics, National Academy of Sciences of Ukraine, Kyiv (Ukraine); Danilov, V. I. [Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv (Ukraine)

    2016-02-01

    To elucidate the effect of radicals on DNA base pairs, we investigated the attacking mechanism of OH and H radicals to the G-C and A-T base pairs, using the density functional theory (DFT) calculations in water approximated by the continuum solvation model. The DFT calculations revealed that the OH radical abstracts the hydrogen atom of a NH{sub 2} group of G or A base and induces a tautomeric reaction for an A-T base pair more significantly than for a G-C base pair. On the other hand, the H radical prefers to bind to the Cytosine NH{sub 2} group of G-C base pair and induce a tautomeric reaction from G-C to G*-C*, whose activation free energy is considerably small (−0.1 kcal/mol) in comparison with that (42.9 kcal/mol) for the reaction of an A-T base pair. Accordingly, our DFT calculations elucidated that OH and H radicals have a significant effect on A-T and G-C base pairs, respectively. This finding will be useful for predicting the effect of radiation on the genetic information recorded in the base sequences of DNA duplexes.

  17. DFT study on the attacking mechanisms of H and OH radicals to G-C and A-T base pairs in water

    International Nuclear Information System (INIS)

    Okutsu, N.; Shimamura, K.; Shimizu, E.; Kurita, N.; Shulga, S.; Danilov, V. I.

    2016-01-01

    To elucidate the effect of radicals on DNA base pairs, we investigated the attacking mechanism of OH and H radicals to the G-C and A-T base pairs, using the density functional theory (DFT) calculations in water approximated by the continuum solvation model. The DFT calculations revealed that the OH radical abstracts the hydrogen atom of a NH 2 group of G or A base and induces a tautomeric reaction for an A-T base pair more significantly than for a G-C base pair. On the other hand, the H radical prefers to bind to the Cytosine NH 2 group of G-C base pair and induce a tautomeric reaction from G-C to G*-C*, whose activation free energy is considerably small (−0.1 kcal/mol) in comparison with that (42.9 kcal/mol) for the reaction of an A-T base pair. Accordingly, our DFT calculations elucidated that OH and H radicals have a significant effect on A-T and G-C base pairs, respectively. This finding will be useful for predicting the effect of radiation on the genetic information recorded in the base sequences of DNA duplexes

  18. 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

  19. The Influence of Square Planar Platinum Complexes on DNA Bases Pairing. An ab initio DFT Study

    Czech Academy of Sciences Publication Activity Database

    Burda, J. V.; Šponer, Jiří; Leszczynski, J.

    2001-01-01

    Roč. 3, č. 19 (2001), s. 4404-4411 ISSN 1463-9076 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA base pairing * platinated base pairs * ab initio DFT study Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.787, year: 2001

  20. 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

  1. 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.

  2. Matrix-Vector Based Fast Fourier Transformations on SDR Architectures

    Directory of Open Access Journals (Sweden)

    Y. He

    2008-05-01

    Full Text Available Today Discrete Fourier Transforms (DFTs are applied in various radio standards based on OFDM (Orthogonal Frequency Division Multiplex. It is important to gain a fast computational speed for the DFT, which is usually achieved by using specialized Fast Fourier Transform (FFT engines. However, in face of the Software Defined Radio (SDR development, more general (parallel processor architectures are often desirable, which are not tailored to FFT computations. Therefore, alternative approaches are required to reduce the complexity of the DFT. Starting from a matrix-vector based description of the FFT idea, we will present different factorizations of the DFT matrix, which allow a reduction of the complexity that lies between the original DFT and the minimum FFT complexity. The computational complexities of these factorizations and their suitability for implementation on different processor architectures are investigated.

  3. 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.

  4. 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.

  5. 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.

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

    Science.gov (United States)

    Jover, Jesús

    2017-11-08

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

  7. 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

  8. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-06-21

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

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

    Science.gov (United States)

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

    2018-06-01

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

  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. Advances in Computational High-Resolution Mechanical Spectroscopy HRMS Part I: Logarithmic Decrement

    International Nuclear Information System (INIS)

    Majewski, M; Magalas, L B; Piłat, A

    2012-01-01

    The comparison between different methods used to compute the logarithmic decrement in high-resolution mechanical spectroscopy (HRMS) is analyzed. The performance of parametric OMI method (Optimization in Multiple Intervals) and interpolated discrete Fourier transform (IpDFT) methods are investigated as a function of the sampling frequency used to digitize free decaying oscillations in low-frequency resonant mechanical spectrometers. It is clearly demonstrated that a new Yoshida-Magalas (YM) method is the most powerful IpDFT-based method which outperforms the standard Yoshida (Y) method and other DFT-based methods. Four IpDFT methods and the OMI method are carefully analyzed as a function of the sampling frequency. The results presented in this work clearly show that the relative error in the estimation of the logarithmic decrement depends both on the length of free decaying signal and on the sampling frequency. The effect of the sampling frequency was not yet reported in the literature. The performance of different methods used in the computations of the logarithmic decrement can be listed in the following order: (1) the OMI, (2) the Yoshida-Magalas YM, (3) the Yoshida-Magalas YMC, and finally (4) the Yoshida Y.

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

    Directory of Open Access Journals (Sweden)

    El Alamy Aziz

    2017-07-01

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

  14. 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.

  15. 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.

  16. RHF and DFT study of the optimized molecular structure and atomic ...

    African Journals Online (AJOL)

    Restricted HartreeFock (RHF) and Density Functional Theory (DFT) studies were carried out on the organic semi conductor material Pentacene. 6-31G and 6-31G* basis sets were used to optimize the molecule and compute the charge distribution at both levels of theory. The results show that the Carbon-Hydrogen bonds in ...

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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)

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  5. 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-based

  6. 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.

  7. 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.

  8. 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.

  9. 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...

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

    Science.gov (United States)

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

    2017-10-01

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

  11. Versatile Density Functionals for Computational Surface Science

    DEFF Research Database (Denmark)

    Wellendorff, Jess

    Density functional theory (DFT) emerged almost 50 years ago. Since then DFT has established itself as the central electronic structure methodology for simulating atomicscale systems from a few atoms to a few hundred atoms. This success of DFT is due to a very favorable accuracy-to-computational c......Density functional theory (DFT) emerged almost 50 years ago. Since then DFT has established itself as the central electronic structure methodology for simulating atomicscale systems from a few atoms to a few hundred atoms. This success of DFT is due to a very favorable accuracy...... resampling techniques, thereby systematically avoiding problems with overfitting. The first ever density functional presenting both reliable accuracy and convincing error estimation is generated. The methodology is general enough to be applied to more complex functional forms with higher-dimensional fitting...

  12. 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.

  13. 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.

  14. 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

  15. Water at silica/liquid water interfaces investigated by DFT-MD simulations

    Science.gov (United States)

    Gaigeot, Marie-Pierre

    This talk is dedicated to probing the microscopic structural organization of water at silica/liquid water interfaces including electrolytes by first principles DFT-based molecular dynamics simulations (DFT-MD). We will present our very recent DFT-MD simulations of electrolytic (KCl, NaCl, NaI) silica/liquid water interfaces in order to unravel the intertwined structural properties of water and electrolytes at the crystalline quartz/liquid water and amorphous silica/liquid water interfaces. DFT-MD simulations provide direct knowledge of the structural organization of water and the H-Bond network formed between the water molecules within the different water layers above the silica surface. One can furthermore extract vibrational signatures of the water molecules within the interfacial layers from the DFT-MD simulations, especially non-linear SFG (Sum Frequency generation) signatures that are active at solid/liquid interfaces. The strength of the simulated spectra is that a detailed analysis of the signatures in terms of the water/water H-Bond networks formed within the interfacial water layers and in terms of the water/silica or water/electrolytes H-Bond networks can be given. Comparisons of SFG spectra between quartz/water/electrolytes and amorphous silica/water/electrolytes interfaces allow us to definitely conclude on how the structural arrangements of liquid water at these electrolytic interfaces modulate the final spectroscopic signatures. Invited speaker.

  16. Symmetry properties of the electron density and following from it limits on the KS-DFT applications

    Science.gov (United States)

    Kaplan, Ilya G.

    2018-03-01

    At present, the Density Functional Theory (DFT) approach elaborated by Kohn with co-authors more than 50 years ago became the most widely used method for study molecules and solids. Using modern computation facilities, it can be applied to systems with million atoms. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this report, I will discuss two cases when the conventional DFT approaches, using only electron density ρ and its gradients, cannot be applied (I will not consider the Ψ-versions of DFT). The first case is quite evident. In the degenerated states, the electron density may not be defined, since electronic and nuclear motions cannot be separated, the vibronic interaction mixed them. The second case is related to the spin of the state. As it was rigorously proved by group theoretical methods at the theorem level, the electron density does not depend on the total spin S of the arbitrary N-electron state. It means that the Kohn-Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, taking into account spin, shows that they modified only exchange functionals, the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin cannot be defined in the framework of the electron density formalism, which corresponds to the one-particle reduced density matrix. This is the main reason of the problems arising in the study by DFT of magnetic properties of the transition metals. The possible way of resolving these problems can be found in the two-particle reduced density matrix formulation of DFT.

  17. 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.

  18. 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...

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

    Science.gov (United States)

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

    2018-04-01

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

  20. Spectroscopic investigation on structure (monomer and dimer), molecular characteristics and comparative study on vibrational analysis of picolinic and isonicotinic acids using experimental and theoretical (DFT & IVP) methods

    Science.gov (United States)

    Ramesh, Gaddam; Reddy, Byru Venkatram

    2018-05-01

    In this investigation, the monomeric structure is determined for picolinic and isonicotinic acids based on geometry optimization for one of the four possible conformers and intramolecular hydrogen bond of Osbnd H⋯O using density functional theory (DFT) employing B3LYP functional supplemented with 6-311++G(d,p) basis set. Using this optimized monomeric form, the dimer structure is determined based on minimum energy and length of hydrogen bonds obtained for two possible dimeric forms yielded due to head-to-tail intermolecular Osbnd H⋯N hydrogen bond (dimer 1) linkage and tail-to -tail intermolecular Osbnd H⋯O hydrogen bond (dimer 2) linkage between pyridine ring and carboxyl group. The structure parameters obtained for monomer and dimer forms are in good agreement with the experimental literature values. The vibrational assignments have been made unambiguously for all the vibrations from FTIR and FT-Raman spectra based on the potential energy distribution (PED) and eigen vectors obtained in DFT and inverse vibrational problem (IVP) computations. The rms error between the observed and scaled frequencies is 7.7 and 9.4 cm-1 for PIA and INA, respectively. A 74-element modified valence force field is derived by Wilson's GF matrix method using 58 experimental frequencies of the two molecules in overlay least-squares technique. The average error between observed and computed frequencies by this method is calculated to be 10.39 cm-1. The results of both DFT and IVP computations yielded good agreement between observed and calculated frequencies. The NLO behaviour using hyperpolarizability values; and HOMO and LUMO energies; of the two molecules are investigated by DFT. Charge density distribution and site of chemical reactivity of the molecules are studied by molecular electrostatic surface potential (MESP). Stability of the molecules arising from hyper conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO

  1. 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.

  2. Excited-state properties from ground-state DFT descriptors: A QSPR approach for dyes.

    Science.gov (United States)

    Fayet, Guillaume; Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Rotureau, Patricia; Adamo, Carlo

    2010-02-26

    This work presents a quantitative structure-property relationship (QSPR)-based approach allowing an accurate prediction of the excited-state properties of organic dyes (anthraquinones and azobenzenes) from ground-state molecular descriptors, obtained within the (conceptual) density functional theory (DFT) framework. The ab initio computation of the descriptors was achieved at several levels of theory, so that the influence of the basis set size as well as of the modeling of environmental effects could be statistically quantified. It turns out that, for the entire data set, a statistically-robust four-variable multiple linear regression based on PCM-PBE0/6-31G calculations delivers a R(adj)(2) of 0.93 associated to predictive errors allowing for rapid and efficient dye design. All the selected descriptors are independent of the dye's family, an advantage over previously designed QSPR schemes. On top of that, the obtained accuracy is comparable to the one of the today's reference methods while exceeding the one of hardness-based fittings. QSPR relationships specific to both families of dyes have also been built up. This work paves the way towards reliable and computationally affordable color design for organic dyes. Copyright 2009 Elsevier Inc. All rights reserved.

  3. 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

  4. Improving Performance and Versatility of Systems Based on Single-Frequency DFT Detectors Such as AD5933

    Directory of Open Access Journals (Sweden)

    Leonid Matsiev

    2014-12-01

    Full Text Available Turning grand concepts such as the Internet of Things (IoT and Smart Cities into reality requires the development and deployment of a wide variety of computing devices incorporated into the Internet infrastructure. Unsupervised sensing is the cornerstone capability that these devices must have to perform useful functions, while also having low cost of acquisition and ownership, little energy consumption and a small footprint. Impedimetric sensing systems based on the so-called single-frequency DFT detectors possess many of these desirable attributes and are often introduced in remote monitoring and wearable devices. This study presents new methods of improving performance of such detectors. It demonstrates that the main source of systematic errors is the discontinuous test phasor causing the crosstalk between the in-phase and quadrature outputs and the leakage of the input signal. The study derives expressions for these errors as a function of the number of samples and operating frequency, and provides methods for correction. The proposed methods are applied to the operation of a practical device—a network analyzer integrated circuit AD5933—and discussed in detail. These methods achieve complete elimination of leakage errors and expansion of the low limit of the operation frequency range by nearly two decades without additional hardware.

  5. 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.

  6. 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.

  7. Simplified DFT methods for consistent structures and energies of large systems

    Science.gov (United States)

    Caldeweyher, Eike; Gerit Brandenburg, Jan

    2018-05-01

    Kohn–Sham density functional theory (DFT) is routinely used for the fast electronic structure computation of large systems and will most likely continue to be the method of choice for the generation of reliable geometries in the foreseeable future. Here, we present a hierarchy of simplified DFT methods designed for consistent structures and non-covalent interactions of large systems with particular focus on molecular crystals. The covered methods are a minimal basis set Hartree–Fock (HF-3c), a small basis set screened exchange hybrid functional (HSE-3c), and a generalized gradient approximated functional evaluated in a medium-sized basis set (B97-3c), all augmented with semi-classical correction potentials. We give an overview on the methods design, a comprehensive evaluation on established benchmark sets for geometries and lattice energies of molecular crystals, and highlight some realistic applications on large organic crystals with several hundreds of atoms in the primitive unit cell.

  8. 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 ...

  9. 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.

  10. Stepwise or concerted? DFT study on the mechanism of ionic Diels-Alder reaction of chromanes

    Directory of Open Access Journals (Sweden)

    Haghdadi Mina

    2016-01-01

    Full Text Available The stepwise and concerted Ionic Diels-Alder reaction between phenyl (pyridin-2-ylmethylene oxonium and styrene derivatives are explored using theoretical method. The results support using computational method via persistent intermediates. The DFT method was essential to reproduce a reasonable potential energy surface for these challenging systems.

  11. 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.

  12. 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.

  13. 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)

  14. 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)

  15. Structure prediction of nanoclusters; a direct or a pre-screened search on the DFT energy landscape?

    Science.gov (United States)

    Farrow, M R; Chow, Y; Woodley, S M

    2014-10-21

    The atomic structure of inorganic nanoclusters obtained via a search for low lying minima on energy landscapes, or hypersurfaces, is reported for inorganic binary compounds: zinc oxide (ZnO)n, magnesium oxide (MgO)n, cadmium selenide (CdSe)n, and potassium fluoride (KF)n, where n = 1-12 formula units. The computational cost of each search is dominated by the effort to evaluate each sample point on the energy landscape and the number of required sample points. The effect of changing the balance between these two factors on the success of the search is investigated. The choice of sample points will also affect the number of required data points and therefore the efficiency of the search. Monte Carlo based global optimisation routines (evolutionary and stochastic quenching algorithms) within a new software package, viz. Knowledge Led Master Code (KLMC), are employed to search both directly and after pre-screening on the DFT energy landscape. Pre-screening includes structural relaxation to minimise a cheaper energy function - based on interatomic potentials - and is found to improve significantly the search efficiency, and typically reduces the number of DFT calculations required to locate the local minima by more than an order of magnitude. Although the choice of functional form is important, the approach is robust to small changes to the interatomic potential parameters. The computational cost of initial DFT calculations of each structure is reduced by employing Gaussian smearing to the electronic energy levels. Larger (KF)n nanoclusters are predicted to form cuboid cuts from the rock-salt phase, but also share many structural motifs with (MgO)n for smaller clusters. The transition from 2D rings to 3D (bubble, or fullerene-like) structures occur at a larger cluster size for (ZnO)n and (CdSe)n. Differences between the HOMO and LUMO energies, for all the compounds apart from KF, are in the visible region of the optical spectrum (2-3 eV); KF lies deep in the UV region

  16. Optical Absorption and Electron Injection of 4-(Cyanomethylbenzoic Acid Based Dyes: A DFT Study

    Directory of Open Access Journals (Sweden)

    Yuehua Zhang

    2015-01-01

    Full Text Available Density functional theory (DFT and time-dependent density functional theory (TDDFT calculations were carried out to study the ground state geometries, electronic structures, and absorption spectra of 4-(cyanomethylbenzoic acid based dyes (AG1 and AG2 used for dye-sensitized solar cells (DSSCs. The excited states properties and the thermodynamical parameters of electron injection were studied. The results showed that (a two dyes have uncoplanar structures along the donor unit and conjugated bridge space, (b two sensitizers exhibited intense absorption in the UV-Vis region, and (c the excited state oxidation potential was higher than the conduction band edge of TiO2 photoanode. As a result, a solar cell based on the 4-(cyanomethylbenzoic acid based dyes exhibited well photovoltaic performance. Furthermore, nine dyes were designed on the basis of AG1 and AG2 to improve optical response and electron injection.

  17. Coherent optical DFT-spread OFDM transmission using orthogonal band multiplexing.

    Science.gov (United States)

    Yang, Qi; He, Zhixue; Yang, Zhu; Yu, Shaohua; Yi, Xingwen; Shieh, William

    2012-01-30

    Coherent optical OFDM (CO-OFDM) combined with orthogonal band multiplexing provides a scalable and flexible solution for achieving ultra high-speed rate. Among many CO-OFDM implementations, digital Fourier transform spread (DFT-S) CO-OFDM is proposed to mitigate fiber nonlinearity in long-haul transmission. In this paper, we first illustrate the principle of DFT-S OFDM. We then experimentally evaluate the performance of coherent optical DFT-S OFDM in a band-multiplexed transmission system. Compared with conventional clipping methods, DFT-S OFDM can reduce the OFDM peak-to-average power ratio (PAPR) value without suffering from the interference of the neighboring bands. With the benefit of much reduced PAPR, we successfully demonstrate 1.45 Tb/s DFT-S OFDM over 480 km SSMF transmission.

  18. 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.

  19. 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.

  20. Water dissociation and CO oxidation over Au/anatase catalyst. A DFT-D2 study

    Science.gov (United States)

    Saqlain, Muhammad Adnan; Hussain, Akhtar; Siddiq, Muhammad; Leitão, Alexandre A.

    2018-03-01

    With the help of DFT-D2 methodology, we have investigated the adsorption of water on clean anatase(001) and Au/anatase(001). In the former case, adsorption energies of H2O differ to small extent computed employing GGA = PW91 and DFT-D2 methods. While the GGA = PW91 predicts that water would desorb close to 650 K on the TiO2 surface, the DFT-D2 predicts that desorption is most likely to occur above 700 K. A comparison of water adsorption on TiO2 and Au/TiO2 surfaces shows that the TiO2 prefers dimer adsorption whereas the Au/TiO2 prefers monomer adsorption. We found that the diffusion of surface hydroxyls on to the Au cluster from the Au/TiO2 periphery is unlikely and it seems that the CO oxidation would occur at the Au/TiO2 boundary. The results show that water dissociation and CO oxidation steps occur easily on Au/TiO2 indicating that this could be good alternative catalyst for water gas shift reaction industry.

  1. 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

  2. Comparison of discrete Fourier transform (DFT) and principal component analysis/DFT as forecasting tools for absorbance time series received by UV-visible probes installed in urban sewer systems.

    Science.gov (United States)

    Plazas-Nossa, Leonardo; Torres, Andrés

    2014-01-01

    The objective of this work is to introduce a forecasting method for UV-Vis spectrometry time series that combines principal component analysis (PCA) and discrete Fourier transform (DFT), and to compare the results obtained with those obtained by using DFT. Three time series for three different study sites were used: (i) Salitre wastewater treatment plant (WWTP) in Bogotá; (ii) Gibraltar pumping station in Bogotá; and (iii) San Fernando WWTP in Itagüí (in the south part of Medellín). Each of these time series had an equal number of samples (1051). In general terms, the results obtained are hardly generalizable, as they seem to be highly dependent on specific water system dynamics; however, some trends can be outlined: (i) for UV range, DFT and PCA/DFT forecasting accuracy were almost the same; (ii) for visible range, the PCA/DFT forecasting procedure proposed gives systematically lower forecasting errors and variability than those obtained with the DFT procedure; and (iii) for short forecasting times the PCA/DFT procedure proposed is more suitable than the DFT procedure, according to processing times obtained.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

  4. Combined UMC- DFT prediction of electron-hole coupling in unit cells of pentacene crystals.

    Science.gov (United States)

    Leal, Luciano Almeida; de Souza Júnior, Rafael Timóteo; de Almeida Fonseca, Antonio Luciano; Ribeiro Junior, Luiz Antonio; Blawid, Stefan; da Silva Filho, Demetrio Antonio; da Cunha, Wiliam Ferreira

    2017-05-01

    Pentacene is an organic semiconductor that draws special attention from the scientific community due to the high mobility of its charge carriers. As electron-hole interactions are important aspects in the regard of such property, a computationally inexpensive method to predict the coupling between these quasi-particles is highly desired. In this work, we propose a hybrid methodology of combining Uncoupled Monte Carlo Simulations (UMC) and Density functional Theory (DFT) methodologies to obtain a good compromise between computational feasibility and accuracy. As a first step in considering a Pentacene crystal, we describe its unit cell: the Pentacene Dimer. Because many conformations can be encountered for the dimer and considering the complexity of the system, we make use of UMC in order to find the most probable structures and relative orientations for the Pentacene-Pentacene complex. Following, we carry out electronic structure calculations in the scope of DFT with the goal of describing the electron-hole coupling on the most probable configurations obtained by UMC. The comparison of our results with previously reported data on the literature suggests that the methodology is well suited for describing transfer integrals of organic semiconductors. The observed accuracy together with the smaller computational cost required by our approach allows us to conclude that such methodology might be an important tool towards the description of systems with higher complexity.

  5. DFT-based prediction of reactivity of short-chain alcohol dehydrogenase

    Science.gov (United States)

    Stawoska, I.; Dudzik, A.; Wasylewski, M.; Jemioła-Rzemińska, M.; Skoczowski, A.; Strzałka, K.; Szaleniec, M.

    2017-06-01

    The reaction mechanism of ketone reduction by short chain dehydrogenase/reductase, ( S)-1-phenylethanol dehydrogenase from Aromatoleum aromaticum, was studied with DFT methods using cluster model approach. The characteristics of the hydride transfer process were investigated based on reaction of acetophenone and its eight structural analogues. The results confirmed previously suggested concomitant transfer of hydride from NADH to carbonyl C atom of the substrate with proton transfer from Tyr to carbonyl O atom. However, additional coupled motion of the next proton in the proton-relay system, between O2' ribose hydroxyl and Tyr154 was observed. The protonation of Lys158 seems not to affect the pKa of Tyr154, as the stable tyrosyl anion was observed only for a neutral Lys158 in the high pH model. The calculated reaction energies and reaction barriers were calibrated by calorimetric and kinetic methods. This allowed an excellent prediction of the reaction enthalpies (R2 = 0.93) and a good prediction of the reaction kinetics (R2 = 0.89). The observed relations were validated in prediction of log K eq obtained for real whole-cell reactor systems that modelled industrial synthesis of S-alcohols.

  6. A new copper(II) Schiff base complex containing asymmetrical tetradentate N.sub.2./sub.O.sub.2./sub. Schiff base ligand: Synthesis, characterization, crystal structure and DFT study

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Baghan, S.H.; Vakili, M.; Khalaji, A.D.; Tahmasebi, V.; Eigner, Václav; Dušek, Michal

    2015-01-01

    Roč. 1082, Feb (2015), 91-96 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Schiff-base * copper (II) * complex * single-crystal * thermal decomposition * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.780, year: 2015

  7. 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.

  8. Diels-Alder reactions for the rational design of benzo[b]thiophenes: DFT-based guidelines for synthetic chemists

    Science.gov (United States)

    Brasca, Romina; Kneeteman, María N.; Mancini, Pedro M. E.; Fabian, Walter M. F.

    2012-02-01

    In this work we studied the capability of several diene/dienophile pairs to undergo Diels-Alder (DA) reactions leading to benzo[b]thiophenes. A variety of synthetically and commercially available nitrothiophenes were chosen as dienophiles. Methyl 5-nitro-3-thiophenecarboxylate was selected as a potential strong electrophilic candidate based on some DFT-based properties and the substitution pattern of the expected product. The mechanistic details concerning the participation of this dienophile in polar DA reactions were investigated through a theoretical point of view. The results were compared with the experimental outcomes. This methodology should allow synthetic chemists to analyze DA reactions in detail in a stage prior to the synthetic job.

  9. 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....

  10. Paper-Based and Computer-Based Concept Mappings: The Effects on Computer Achievement, Computer Anxiety and Computer Attitude

    Science.gov (United States)

    Erdogan, Yavuz

    2009-01-01

    The purpose of this paper is to compare the effects of paper-based and computer-based concept mappings on computer hardware achievement, computer anxiety and computer attitude of the eight grade secondary school students. The students were randomly allocated to three groups and were given instruction on computer hardware. The teaching methods used…

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Chlorophenols Sorption on Multi-Walled Carbon Nanotubes: DFT Modeling and Structure-Property Relationship Analysis

    OpenAIRE

    Watkins, Marquita; Sizochenko, Natalia; Moore, Quentarius; Golebiowski, Marek; Leszczynska, Danuta; Leszczynski, Jerzy

    2017-01-01

    Presence of chlorophenols in drinking water could be hazardous to human health. Optimization and computational modeling of experimental conditions of adsorption lead to understanding the mechanisms of this process and to creating the efficient experimental equipment. In the current study, we investigated multi-walled carbon nanotubes by means of density functional theory (DFT) approach. This is applied to study selected types of interactions between six solvents, five types of nanotubes, and ...

  16. Insight into destabilization mechanism of Mg-based hydrides interstitially co-doped with nonmetals: a DFT study

    Science.gov (United States)

    Wu, Zhen; Zhu, Luying; Yang, Fusheng; Zhang, Zaoxiao; Nyamsi, Serge N.

    2018-04-01

    Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom-1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg-Ni/NiH4 bonds, caused by criss-cross interactions between B-Ni and N-Mg bonds.

  17. Water adsorption on a copper formate paddlewheel model of CuBTC: A comparative MP2 and DFT study

    Science.gov (United States)

    Toda, Jordi; Fischer, Michael; Jorge, Miguel; Gomes, José R. B.

    2013-11-01

    Simultaneous adsorption of two water molecules on open metal sites of the HKUST-1 metal-organic framework (MOF), modeled with a Cu2(HCOO)4 cluster, was studied by means of density functional theory (DFT) and second-order Moller-Plesset (MP2) approaches together with correlation consistent basis sets. Experimental geometries and MP2 energetic data extrapolated to the complete basis set limit were used as benchmarks for testing the accuracy of several different exchange-correlation functionals in the correct description of the water-MOF interaction. M06-L and some LC-DFT methods arise as the most appropriate in terms of the quality of geometrical data, energetic data and computational resources needed.

  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. 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....

  20. Multi-scale multi-physics computational chemistry simulation based on ultra-accelerated quantum chemical molecular dynamics method for structural materials in boiling water reactor

    International Nuclear Information System (INIS)

    Miyamoto, Akira; Sato, Etsuko; Sato, Ryo; Inaba, Kenji; Hatakeyama, Nozomu

    2014-01-01

    In collaboration with experimental experts we have reported in the present conference (Hatakeyama, N. et al., “Experiment-integrated multi-scale, multi-physics computational chemistry simulation applied to corrosion behaviour of BWR structural materials”) the results of multi-scale multi-physics computational chemistry simulations applied to the corrosion behaviour of BWR structural materials. In macro-scale, a macroscopic simulator of anode polarization curve was developed to solve the spatially one-dimensional electrochemical equations on the material surface in continuum level in order to understand the corrosion behaviour of typical BWR structural material, SUS304. The experimental anode polarization behaviours of each pure metal were reproduced by fitting all the rates of electrochemical reactions and then the anode polarization curve of SUS304 was calculated by using the same parameters and found to reproduce the experimental behaviour successfully. In meso-scale, a kinetic Monte Carlo (KMC) simulator was applied to an actual-time simulation of the morphological corrosion behaviour under the influence of an applied voltage. In micro-scale, an ultra-accelerated quantum chemical molecular dynamics (UA-QCMD) code was applied to various metallic oxide surfaces of Fe 2 O 3 , Fe 3 O 4 , Cr 2 O 3 modelled as same as water molecules and dissolved metallic ions on the surfaces, then the dissolution and segregation behaviours were successfully simulated dynamically by using UA-QCMD. In this paper we describe details of the multi-scale, multi-physics computational chemistry method especially the UA-QCMD method. This method is approximately 10,000,000 times faster than conventional first-principles molecular dynamics methods based on density-functional theory (DFT), and the accuracy was also validated for various metals and metal oxides compared with DFT results. To assure multi-scale multi-physics computational chemistry simulation based on the UA-QCMD method for

  1. Communication: Hole localization in Al-doped quartz SiO{sub 2} within ab initio hybrid-functional DFT

    Energy Technology Data Exchange (ETDEWEB)

    Gerosa, Matteo [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Di Valentin, Cristiana; Pacchioni, Gianfranco [Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, via R. Cozzi 55, 20125 Milan (Italy); Bottani, Carlo Enrico, E-mail: carlo.bottani@polimi.it [Department of Energy, Politecnico di Milano, via Ponzio 34/3, 20133 Milano (Italy); Center for Nano Science and Technology @Polimi, Istituto Italiano di Tecnologia, via Pascoli 70/3, 20133 Milano (Italy); Onida, Giovanni [Dipartimento di Fisica dell’ Universita’ degli Studi di Milano and European Theoretical Spectroscopy Facility (ETSF), Via Celoria 16, 20133 Milan (Italy)

    2015-09-21

    We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO{sub 2}, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators.

  2. 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

  3. 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.

  4. 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.

  5. DFT study of the mechanism and stereoselectivity of the 1,3-dipolar ...

    Indian Academy of Sciences (India)

    and methyl acrylate) using DFT method. An ana- lysis of ..... field (SCRF)30,46 model based on the polarizable con- tinuum model (PCM) of Tomasi's group47 have been applied. ... stereoselectivity relative to the gas-phase since the trends of ...

  6. Computational prediction of the pKas of small peptides through Conceptual DFT descriptors

    Science.gov (United States)

    Frau, Juan; Hernández-Haro, Noemí; Glossman-Mitnik, Daniel

    2017-03-01

    The experimental pKa of a group of simple amines have been plotted against several Conceptual DFT descriptors calculated by means of different density functionals, basis sets and solvation schemes. It was found that the best fits are those that relate the pKa of the amines with the global hardness η through the MN12SX density functional in connection with the Def2TZVP basis set and the SMD solvation model, using water as a solvent. The parameterized equation resulting from the linear regression analysis has then been used for the prediction of the pKa of small peptides of interest in the study of diabetes and Alzheimer disease. The accuracy of the results is relatively good, with a MAD of 0.36 units of pKa.

  7. Spectroscopic analysis of 8-hydroxyquinoline derivatives and investigation of its reactive properties by DFT and molecular dynamics simulations

    Science.gov (United States)

    Sureshkumar, B.; Mary, Y. Sheena; Resmi, K. S.; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, C.; Narayana, B.; Suma, S.

    2018-03-01

    Two 8-hydroxyquinoline derivatives, 5,7-dichloro-8-hydroxyquinoline (57DC8HQ) and 5-chloro-7-iodo-8-hydroxy quinoline (5CL7I8HQ) have been investigated in details by means of spectroscopic characterization and computational molecular modelling techniques. FT-IR and FT-Raman experimental spectroscopic approaches have been utilized in order to obtain detailed spectroscopic signatures of title compounds, while DFT calculations have been used in order to visualize and assign vibrations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the title molecules exhibit NLO properties. The evaluated HOMO and LUMO energies demonstrate the chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyperconjugative interactions and charge delocalization. DFT calculations have been also used jointly with MD simulations in order to investigate in details global and local reactivity properties of title compounds. Also, molecular docking has been also used in order to investigate affinity of title compounds against decarboxylase inhibitor and quinoline derivatives can be a lead compounds for developing new antiparkinsonian drug.

  8. Spectroscopic (FT-IR, FT-Raman, UV, 1H and 13C NMR insights, electronic profiling and DFT computations on ({(E-[3-(1H-imidazol-1-yl-1-phenylpropylidene] amino}oxy(4-nitrophenylmethanone, an imidazole-bearing anti-Candida agent

    Directory of Open Access Journals (Sweden)

    Al-Wahaibi Lamya H.

    2018-02-01

    Full Text Available The anti-Candida agent, ({(E-[3-(1H-imidazol-1-yl-1-phenylpropylidene]amnio}oxy(4-nitropheny methanone (IPAONM, was subjected to comprehensive spectroscopic (FT-IR, FT-Raman, UV–Vis 1H and 13C NMR characterization as well as Hartree Fock and density functional theory computation studies. The selected optimized geometric bond lengths and bond angles of the IPAONM molecule were compared with the experimental values. The calculated wavenumbers have been scaled and compared with the experimental spectra. Mulliken charges and natural bond orbital analysis of the title molecule were calculated and interpreted. The energy and oscillator strengths of the IPAONM molecule were calculated by time-dependent density functional theory (TD-DFT. In addition, frontier molecular orbitals and molecular electrostatic potential diagram of the title compound were computed and analyzed. A study on the electronic properties, such as HOMO, HOMO-1, LUMO and LUMO+1 energies was carried out using TD-DFT approach. The 1H and 13C NMR chemical shift values of the title compound were calculated by the gauge independent atomic orbital method and compared with the experimental results.

  9. Molecular structure, vibrational spectra and DFT computational studies of melaminium N-acetylglycinate dihydrate

    Science.gov (United States)

    Tanak, H.; Pawlus, K.; Marchewka, M. K.

    2016-10-01

    Melaminium N-acetylglycinate dihydrate, an organic material has been synthesized and characterized by X-ray diffraction, FT-IR, and FT-Raman spectroscopies for the protiated and deuteriated crystals. The title complex crystallizes in the triclinic system, and the space group is P-1 with a = 5.642(1) Å, b = 7.773(2) Å, c = 15.775(3) Å, α = 77.28(1)°, β = 84.00(1)°, γ = 73.43(1)° and Z = 2. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional method (B3LYP) with the 6-311++G(d,p) basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. The intermolecular hydrogen bonding interactions of the title compound have been investigated using the natural bonding orbital analysis. It reveals that the O-H···O, N-H···N and N-H···O intermolecular interactions significantly influence crystal packing of this molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, thermodynamic properties, frontier orbitals and chemical reactivity descriptors were also performed at 6-311++G(d,p) level of theory.

  10. Quantum fluid dynamics based current-density functional study of a helium atom in a strong time-dependent magnetic field

    International Nuclear Information System (INIS)

    Vikas

    2011-01-01

    Evolution of the helium atom in a strong time-dependent (TD) magnetic field (B) of strength up to 10 11 G is investigated through a quantum fluid dynamics (QFD) based current-density functional theory (CDFT). The TD-QFD-CDFT computations are performed through numerical solution of a single generalized nonlinear Schroedinger equation employing vector exchange-correlation potentials and scalar exchange-correlation density functionals that depend both on the electronic charge-density and the current-density. The results are compared with that obtained from a B-TD-QFD-DFT approach (based on conventional TD-DFT) under similar numerical constraints but employing only scalar exchange-correlation potential dependent on electronic charge-density only. The B-TD-QFD-DFT approach, at a particular TD magnetic field-strength, yields electronic charge- and current-densities as well as exchange-correlation potential resembling with that obtained from the time-independent studies involving static (time-independent) magnetic fields. However, TD-QFD-CDFT electronic charge- and current-densities along with the exchange-correlation potential and energy differ significantly from that obtained using B-TD-QFD-DFT approach, particularly at field-strengths >10 9 G, representing dynamical effects of a TD field. The work concludes that when a helium atom is subjected to a strong TD magnetic field of order >10 9 G, the conventional TD-DFT based approach differs 'dynamically' from the CDFT based approach under similar computational constraints. (author)

  11. DFT Simulation of Structural and Optical Properties of 9-Aminoacridine Half-Sandwich Ru(II), Rh(III), and Ir(III) Antitumoral Complexes and Their Interaction with DNA.

    Science.gov (United States)

    Cerón-Carrasco, José Pedro; Ruiz, José; Vicente, Consuelo; de Haro, Concepción; Bautista, Delia; Zúñiga, José; Requena, Alberto

    2017-08-08

    In this work, we use DFT-based methods to simulate the chemical structures, optical properties, and interaction with DNA of a recently synthesized chelated C^N 9-aminoacridine arene Ru(II) anticancer agent and two new closely related Rh(III) and Ir(III) complexes using DFT-based methods. Four chemical models and a number of theoretical approaches, which representatively include the PBE0, B97D, ωB97X, ωB97X-D, M06, and M06-L density functionals and the LANL2DZ, def2-SVP, and def2-TZVP basis sets, are tested. The best overall accuracy/cost performance for the optimization process is reached at the ωB97X-D/def2-SVP and M06/def2-SVP levels of theory. Inclusion of explicit solvent molecules (CHCl 3 ) further refines the geometry, while taking into account the crystal network gives no significant improvements of the computed bond distances and angles. The analysis of the excited states reveals that the M06 level matches better the experimental absorption spectra, compared to ωB97X-D. The use of the M06/def2-SVP approach is therefore a well-balanced method to study theoretically the bioactivity of this type of antitumoral complexes, so we couple this TD-DFT approach to molecular dynamics simulations in order to assess their reactivity with DNA. The reported results demonstrate that these drugs could be used to inject electrons into DNA, which might broaden their applications in photoactivated chemotherapy and as new materials for DNA-based electrochemical nanodevices.

  12. ABINIT: Plane-Wave-Based Density-Functional Theory on High Performance Computers

    Science.gov (United States)

    Torrent, Marc

    2014-03-01

    For several years, a continuous effort has been produced to adapt electronic structure codes based on Density-Functional Theory to the future computing architectures. Among these codes, ABINIT is based on a plane-wave description of the wave functions which allows to treat systems of any kind. Porting such a code on petascale architectures pose difficulties related to the many-body nature of the DFT equations. To improve the performances of ABINIT - especially for what concerns standard LDA/GGA ground-state and response-function calculations - several strategies have been followed: A full multi-level parallelisation MPI scheme has been implemented, exploiting all possible levels and distributing both computation and memory. It allows to increase the number of distributed processes and could not be achieved without a strong restructuring of the code. The core algorithm used to solve the eigen problem (``Locally Optimal Blocked Congugate Gradient''), a Blocked-Davidson-like algorithm, is based on a distribution of processes combining plane-waves and bands. In addition to the distributed memory parallelization, a full hybrid scheme has been implemented, using standard shared-memory directives (openMP/openACC) or porting some comsuming code sections to Graphics Processing Units (GPU). As no simple performance model exists, the complexity of use has been increased; the code efficiency strongly depends on the distribution of processes among the numerous levels. ABINIT is able to predict the performances of several process distributions and automatically choose the most favourable one. On the other hand, a big effort has been carried out to analyse the performances of the code on petascale architectures, showing which sections of codes have to be improved; they all are related to Matrix Algebra (diagonalisation, orthogonalisation). The different strategies employed to improve the code scalability will be described. They are based on an exploration of new diagonalization

  13. Fabrication of an electrochemical sensor based on computationally designed molecularly imprinted polymer for the determination of mesalamine in real samples

    Energy Technology Data Exchange (ETDEWEB)

    Torkashvand, M. [Department of Analytical Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Gholivand, M.B., E-mail: mbgholivand@yahoo.com [Department of Analytical Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Taherkhani, F. [Department of Physical Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of)

    2015-10-01

    A novel electrochemical sensor based on mesalamine molecularly imprinted polymer (MIP) film on a glassy carbon electrode was fabricated. Density functional theory (DFT) in gas and solution phases was developed to study the intermolecular interactions in the pre-polymerization mixture and to find the suitable functional monomers in MIP preparation. On the basis of computational results, o-phenylenediamine (OP), gallic acid (GA) and p-aminobenzoic acid (ABA) were selected as functional monomers. The MIP film was cast on glassy carbon electrode by electropolymerization of solution containing ternary monomers and then followed by Ag dendrites (AgDs) with nanobranch deposition. The surface feature of the modified electrode (AgDs/MIP/GCE) was characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Under the optimal experimental conditions, the peak current was proportional to the concentration of mesalamine ranging from 0.05 to 100 μM, with the detection limit of 0.015 μM. The proposed sensor was applied successfully for mesalamine determination in real samples. - Highlights: • The determination of MES using AgDs/MIP/GCE is reported for the first time. • The computer assisted design of terpolymer MIPs was used to screen monomers. • Theoretical results of DFT approach were in agreement with experimental results. • The sensor displayed a high selectivity for template in the presence of interferes. • The developed sensor has been applied to determine mesalamine in real samples.

  14. Fabrication of an electrochemical sensor based on computationally designed molecularly imprinted polymer for the determination of mesalamine in real samples

    International Nuclear Information System (INIS)

    Torkashvand, M.; Gholivand, M.B.; Taherkhani, F.

    2015-01-01

    A novel electrochemical sensor based on mesalamine molecularly imprinted polymer (MIP) film on a glassy carbon electrode was fabricated. Density functional theory (DFT) in gas and solution phases was developed to study the intermolecular interactions in the pre-polymerization mixture and to find the suitable functional monomers in MIP preparation. On the basis of computational results, o-phenylenediamine (OP), gallic acid (GA) and p-aminobenzoic acid (ABA) were selected as functional monomers. The MIP film was cast on glassy carbon electrode by electropolymerization of solution containing ternary monomers and then followed by Ag dendrites (AgDs) with nanobranch deposition. The surface feature of the modified electrode (AgDs/MIP/GCE) was characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Under the optimal experimental conditions, the peak current was proportional to the concentration of mesalamine ranging from 0.05 to 100 μM, with the detection limit of 0.015 μM. The proposed sensor was applied successfully for mesalamine determination in real samples. - Highlights: • The determination of MES using AgDs/MIP/GCE is reported for the first time. • The computer assisted design of terpolymer MIPs was used to screen monomers. • Theoretical results of DFT approach were in agreement with experimental results. • The sensor displayed a high selectivity for template in the presence of interferes. • The developed sensor has been applied to determine mesalamine in real samples

  15. 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.

  16. A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

    Science.gov (United States)

    Ali, Narmeen; Mansha, Asim; Asim, Sadia; Zahoor, Ameer Fawad; Ghafoor, Sidra; Akbar, Muhammad Usman

    2018-03-01

    This paper deals with combined theoretical and experimental study of geometric, electronic and vibrational properties of 2-chlorothioxanthone (CTX) molecule which is potential photosensitizer. The FT-IR spectrum of CTX in solid phase was recorded in 4000-400 cm-1 region. The UV-Vis. absorption spectrum was also recorded in the laboratory as well as computed at DFT/B3LYP level in five different phases viz. gas, water, DMSO, acetone and ethanol. The quantum mechanics based theoretical IR and Raman spectra were also calculated for the title compound employing HF and DFT functional with 3-21G+, 6-31G+ and 6-311G+, 6-311G++ basis sets, respectively, and assignment of each vibrational frequency has been done on the basis of potential energy distribution (PED). A comparison has been made between theoretical and experimental vibrational spectra as well as for the UV-Vis. absorption spectra. The computed infra red & Raman spectra by DFT compared with experimental spectra along with reliable vibrational assignment based on PED. The calculated electronic properties, results of natural bonding orbital (NBO) analysis, charge distribution, dipole moment and energies have been reported in the paper. Bimolecular quenching of triplet state of CTX in the presence of triethylamine, 2-propanol triethylamine and diazobicyclooctane (DABCO) reflect the interactions between them. The bimolecular quenching rate constant is fastest for interaction of 3CTX in the presence of DABCO reflecting their stronger interactions.

  17. 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.

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

    Science.gov (United States)

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

    2014-06-01

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

  19. Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost

    Science.gov (United States)

    Bajaj, Akash; Janet, Jon Paul; Kulik, Heather J.

    2017-11-01

    The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. We select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT.

  20. Large-scale atomistic simulations of nanostructured materials based on divide-and-conquer density functional theory

    Directory of Open Access Journals (Sweden)

    Vashishta P.

    2011-05-01

    Full Text Available A linear-scaling algorithm based on a divide-and-conquer (DC scheme is designed to perform large-scale molecular-dynamics simulations, in which interatomic forces are computed quantum mechanically in the framework of the density functional theory (DFT. This scheme is applied to the thermite reaction at an Al/Fe2O3 interface. It is found that mass diffusion and reaction rate at the interface are enhanced by a concerted metal-oxygen flip mechanism. Preliminary simulations are carried out for an aluminum particle in water based on the conventional DFT, as a target system for large-scale DC-DFT simulations. A pair of Lewis acid and base sites on the aluminum surface preferentially catalyzes hydrogen production in a low activation-barrier mechanism found in the simulations

  1. 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.

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

    Directory of Open Access Journals (Sweden)

    R. Balajee

    2016-01-01

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

  3. 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. 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.

  5. Spectroscopic, Homo-Lumo and NLO studies of tetra fluoro phthalate doped Coumarin crystals using DFT method

    Science.gov (United States)

    Latha, B.; Kumaresan, P.; Nithiyanantham, S.; Sampathkumar, K.

    2017-08-01

    In the present examination, a methodical study has been done on the development of unadulterated and Coumarin doped Tetrafluoro Phthalate precious stones. Powder X-beam diffraction studies were done and the cross section parameters were computed by minimum square technique in pure and doped crystals. FT-IR, UV-Vis, Thermal, Micro-hardness and Dielectric studies were additionally done for the pure and doped crystals. The tentatively watched FT-IR and FT-Raman groups were allotted to various ordinary methods of the atom. The steadiness and charge delocalization of the particle were likewise concentrations were done by characteristic security orbital (NBO) examination. The HOMO-LUMO energies depict the charge exchange happens inside the particle. Atomic electrostatic potential has been broken down the electronic properties such as excitation energies, oscillator quality, wavelengths and HOMO-LUMO energies were acquired by time-subordinate DFT (TD-DFT) approach. The SHG of pure and doped TFP stones were examined through Nd:YAG Q-exchanged laser.

  6. 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.

  7. Matrix-isolation FT-IR and DFT theoretical studies of the intramolecular hydrogen bonding in Mannich bases

    International Nuclear Information System (INIS)

    Pajak, J.; Rospenk, M.; Maes, G.; Sobczyk, L.

    2006-01-01

    FT-IR Ar-matrix isolated spectra were studied for dichloro- (Cl 2 -MB) and tetrachloroderivatives (Cl 4 -MB) of the ortho Mannich base. The spectra were analyzed based on the DFT calculated frequencies and intensities and compared with those recorded in CCl 4 solution in the region of the ν(OH) and ν(OD) vibrations. The matrix-isolated spectra are characterized by narrower ν(OH) and ν(OD) bands with much better resolved fine structure than in solution. The fine structure originates from the anharmonic coupling with the low frequency modes as well as from Fermi resonance. The ν(OD) band shapes can be reproduced exclusively by assuming the Fermi resonance with overtones and summation of the frequencies of modes into which the bridge atoms are involved. The frequency isotopic ratio (ISR) is for both compounds 1.33 while the half-width ratios are equal to 1.82 and 1.94, for Cl 2 -MB and Cl 4 -MB, respectively

  8. 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.

  9. A third-generation density-functional-theory-based method for calculating canonical molecular orbitals of large molecules.

    Science.gov (United States)

    Hirano, Toshiyuki; Sato, Fumitoshi

    2014-07-28

    We used grid-free modified Cholesky decomposition (CD) to develop a density-functional-theory (DFT)-based method for calculating the canonical molecular orbitals (CMOs) of large molecules. Our method can be used to calculate standard CMOs, analytically compute exchange-correlation terms, and maximise the capacity of next-generation supercomputers. Cholesky vectors were first analytically downscaled using low-rank pivoted CD and CD with adaptive metric (CDAM). The obtained Cholesky vectors were distributed and stored on each computer node in a parallel computer, and the Coulomb, Fock exchange, and pure exchange-correlation terms were calculated by multiplying the Cholesky vectors without evaluating molecular integrals in self-consistent field iterations. Our method enables DFT and massively distributed memory parallel computers to be used in order to very efficiently calculate the CMOs of large molecules.

  10. 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.

  11. 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.

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

    Science.gov (United States)

    Sadasivam, K.; Kumaresan, R.

    2011-06-01

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

  13. 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.

  14. Palladium(0) alkyne complexes as active species: A DFT-investigation

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fabrizi, Giancarlo; Cacchi, Sandro

    2005-01-01

    Alkynes have been found to be excellent ligands for Pd(0); the stability of a range of alkyne-Pd(0) complexes, and their reactivity in oxidative addition, have been investigated by DFT methods.......Alkynes have been found to be excellent ligands for Pd(0); the stability of a range of alkyne-Pd(0) complexes, and their reactivity in oxidative addition, have been investigated by DFT methods....

  15. Acidity constants from DFT-based molecular dynamics simulations

    International Nuclear Information System (INIS)

    Sulpizi, Marialore; Sprik, Michiel

    2010-01-01

    In this contribution we review our recently developed method for the calculation of acidity constants from density functional theory based molecular dynamics simulations. The method is based on a half reaction scheme in which protons are formally transferred from solution to the gas phase. The corresponding deprotonation free energies are computed from the vertical energy gaps for insertion or removal of protons. Combined to full proton transfer reactions, the deprotonation energies can be used to estimate relative acidity constants and also the Broensted pK a when the deprotonation free energy of a hydronium ion is used as a reference. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pK a values (20 units). The thermochemical corrections for the biasing potentials assisting and directing the insertion are discussed in some detail.

  16. Ab initio and relativistic DFT study of spin–rotation and NMR shielding constants in XF{sub 6} molecules, X = S, Se, Te, Mo, and W

    Energy Technology Data Exchange (ETDEWEB)

    Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Demissie, Taye B. [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway); Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland); Jaszuński, Michał, E-mail: michal.jaszunski@icho.edu.pl [Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland)

    2014-05-21

    We present an analysis of the spin–rotation and absolute shielding constants of XF{sub 6} molecules (X = S, Se, Te, Mo, W) based on ab initio coupled cluster and four-component relativistic density-functional theory (DFT) calculations. The results show that the relativistic contributions to the spin–rotation and shielding constants are large both for the heavy elements as well as for the fluorine nuclei. In most cases, incorporating the computed relativistic corrections significantly improves the agreement between our results and the well-established experimental values for the isotropic spin–rotation constants and their anisotropic components. This suggests that also for the other molecules, for which accurate and reliable experimental data are not available, reliable values of spin–rotation and absolute shielding constants were determined combining ab initio and relativistic DFT calculations. For the heavy nuclei, the breakdown of the relationship between the spin–rotation constant and the paramagnetic contribution to the shielding constant, due to relativistic effects, causes a significant error in the total absolute shielding constants.

  17. 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....

  18. Aggregation induced emission enhancement of pyrene-appended Schiff base luminophore and its photovoltaic effect

    Energy Technology Data Exchange (ETDEWEB)

    Panda, Uttam; Roy, Suman; Mallick, Debashis [Department of Chemistry, Jadavpur University, Kolkata 700032 (India); Dalapati, Pradip [Condensed Matter Physics Research Center, Department of Physics, Jadavpur University, Kolkata 700032 (India); Biswas, Subir [Immunology Lab, Department of Zoology, University of Calcutta, Kolkata 700019 (India); Manik, Nabin Baran [Condensed Matter Physics Research Center, Department of Physics, Jadavpur University, Kolkata 700032 (India); Bhattacharyya, Arindam [Immunology Lab, Department of Zoology, University of Calcutta, Kolkata 700019 (India); Sinha, Chittaranjan, E-mail: c_r_sinha@yahoo.com [Department of Chemistry, Jadavpur University, Kolkata 700032 (India)

    2016-07-15

    Pyrene appended Schiff base, 1,3-bis-((E)-pyrene-1-ylmethyleneamino)propan-2-ol (HL), a fluorophore, shows aggregation induced emission enhancement upon addition of water in DMF (4:1, v/v) solution; the quantum yield (Φ) is increased by 0.034–0.450. Under illumination of solar radiation HL (10{sup −3} M) impregnated photovoltaic cell generates 4.4 mA/6.29 V electricity. DFT and TD-DFT computation of optimized geometry of HL has explained the photophysical properties.

  19. Disciplines, models, and computers: the path to computational quantum chemistry.

    Science.gov (United States)

    Lenhard, Johannes

    2014-12-01

    Many disciplines and scientific fields have undergone a computational turn in the past several decades. This paper analyzes this sort of turn by investigating the case of computational quantum chemistry. The main claim is that the transformation from quantum to computational quantum chemistry involved changes in three dimensions. First, on the side of instrumentation, small computers and a networked infrastructure took over the lead from centralized mainframe architecture. Second, a new conception of computational modeling became feasible and assumed a crucial role. And third, the field of computa- tional quantum chemistry became organized in a market-like fashion and this market is much bigger than the number of quantum theory experts. These claims will be substantiated by an investigation of the so-called density functional theory (DFT), the arguably pivotal theory in the turn to computational quantum chemistry around 1990.

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

    Science.gov (United States)

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

    2017-11-14

    We investigate the impact of choosing regressors and molecular representations for the construction of fast machine learning (ML) models of 13 electronic ground-state properties of organic molecules. The performance of each regressor/representation/property combination is assessed using learning curves which report out-of-sample errors as a function of training set size with up to ∼118k distinct molecules. Molecular structures and properties at the hybrid density functional theory (DFT) level of theory come from the QM9 database [ Ramakrishnan et al. Sci. Data 2014 , 1 , 140022 ] and include enthalpies and free energies of atomization, HOMO/LUMO energies and gap, dipole moment, polarizability, zero point vibrational energy, heat capacity, and the highest fundamental vibrational frequency. Various molecular representations have been studied (Coulomb matrix, bag of bonds, BAML and ECFP4, molecular graphs (MG)), as well as newly developed distribution based variants including histograms of distances (HD), angles (HDA/MARAD), and dihedrals (HDAD). Regressors include linear models (Bayesian ridge regression (BR) and linear regression with elastic net regularization (EN)), random forest (RF), kernel ridge regression (KRR), and two types of neural networks, graph convolutions (GC) and gated graph networks (GG). Out-of sample errors are strongly dependent on the choice of representation and regressor and molecular property. Electronic properties are typically best accounted for by MG and GC, while energetic properties are better described by HDAD and KRR. The specific combinations with the lowest out-of-sample errors in the ∼118k training set size limit are (free) energies and enthalpies of atomization (HDAD/KRR), HOMO/LUMO eigenvalue and gap (MG/GC), dipole moment (MG/GC), static polarizability (MG/GG), zero point vibrational energy (HDAD/KRR), heat capacity at room temperature (HDAD/KRR), and highest fundamental vibrational frequency (BAML/RF). We present numerical

  1. Development of ab initio techniques critical for future science-based explosives R&D

    Energy Technology Data Exchange (ETDEWEB)

    Wixom, Ryan R. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Mattsson, Ann Elisabet [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2013-10-01

    Density Functional Theory (DFT) has emerged as an indispensable tool in materials research, since it can accurately predict properties of a wide variety of materials at both equilibrium and extreme conditions. However, for organic molecular crystal explosives, successful application of DFT has largely failed due to the inability of current exchange-correlation functionals to correctly describe intermolecular van der Waals (vdWs) forces. Despite this, we have discovered that even with no treatment of vdWs bonding, the AM05 functional and DFT based molecular dynamics (MD) could be used to study the properties of molecular crystals under compression. We have used DFT-MD to predict the unreacted Hugoniots for PETN and HNS and validated the results by comparison with crystalline and porous experimental data. Since we are also interested in applying DFT methods to study the equilibrium volume properties of explosives, we studied the nature of the vdWs bonding in pursuit of creating a new DFT functional capable of accurately describing equilibrium bonding of molecular crystals. In this report we discuss our results for computing shock Hugoniots of molecular crystals and also what was learned about the nature of bonding in these materials.

  2. Capability-based computer systems

    CERN Document Server

    Levy, Henry M

    2014-01-01

    Capability-Based Computer Systems focuses on computer programs and their capabilities. The text first elaborates capability- and object-based system concepts, including capability-based systems, object-based approach, and summary. The book then describes early descriptor architectures and explains the Burroughs B5000, Rice University Computer, and Basic Language Machine. The text also focuses on early capability architectures. Dennis and Van Horn's Supervisor; CAL-TSS System; MIT PDP-1 Timesharing System; and Chicago Magic Number Machine are discussed. The book then describes Plessey System 25

  3. 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.

  4. 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.

  5. Watson-Crick Base Pairing, Electronic and Photophysical Properties of Triazole Modified Adenine Analogues: A Computational Study

    KAUST Repository

    Das, Shubhajit

    2015-09-17

    We employ first-principles Density Functional Theory (DFT) and time-dependent DFT (TDDFT) to elucidate structural, electronic and optical properties of a few recently reported triazole adenine nucleobase analogues. The results are compared against the findings obtained for both natural adenine nucleobase and available experimental data. The optical absorption of these adenine analogues are calculated both in gas-phase and in solvent (methanol) using Polarized Continuum Model (PCM). We find that all the analogues show a red-shifted absorption profile as compared to adenine. Our simulated emission spectra in solvent compare fairly well with experimentally observed results. We investigate base paring ability of these adenine analogues with thymine. The calculations on the intrinsic stability of these base pairs ascertain that all the adenine analogues form the hydrogen bonded Watson-Crick base pair with similar H-bonding energy as obtained for natural adenine-thymine base pair. In our study, we provide a microscopic origin of the low-energy absorption and emission peaks, observed experimentally.

  6. Watson-Crick Base Pairing, Electronic and Photophysical Properties of Triazole Modified Adenine Analogues: A Computational Study

    KAUST Repository

    Das, Shubhajit; Samanta, Pralok Kumar; Pati, Swapan

    2015-01-01

    We employ first-principles Density Functional Theory (DFT) and time-dependent DFT (TDDFT) to elucidate structural, electronic and optical properties of a few recently reported triazole adenine nucleobase analogues. The results are compared against the findings obtained for both natural adenine nucleobase and available experimental data. The optical absorption of these adenine analogues are calculated both in gas-phase and in solvent (methanol) using Polarized Continuum Model (PCM). We find that all the analogues show a red-shifted absorption profile as compared to adenine. Our simulated emission spectra in solvent compare fairly well with experimentally observed results. We investigate base paring ability of these adenine analogues with thymine. The calculations on the intrinsic stability of these base pairs ascertain that all the adenine analogues form the hydrogen bonded Watson-Crick base pair with similar H-bonding energy as obtained for natural adenine-thymine base pair. In our study, we provide a microscopic origin of the low-energy absorption and emission peaks, observed experimentally.

  7. Discrete Fourier Transform Analysis in a Complex Vector Space

    Science.gov (United States)

    Dean, Bruce H.

    2009-01-01

    Alternative computational strategies for the Discrete Fourier Transform (DFT) have been developed using analysis of geometric manifolds. This approach provides a general framework for performing DFT calculations, and suggests a more efficient implementation of the DFT for applications using iterative transform methods, particularly phase retrieval. The DFT can thus be implemented using fewer operations when compared to the usual DFT counterpart. The software decreases the run time of the DFT in certain applications such as phase retrieval that iteratively call the DFT function. The algorithm exploits a special computational approach based on analysis of the DFT as a transformation in a complex vector space. As such, this approach has the potential to realize a DFT computation that approaches N operations versus Nlog(N) operations for the equivalent Fast Fourier Transform (FFT) calculation.

  8. Computational Benchmarking for Ultrafast Electron Dynamics: Wave Function Methods vs Density Functional Theory.

    Science.gov (United States)

    Oliveira, Micael J T; Mignolet, Benoit; Kus, Tomasz; Papadopoulos, Theodoros A; Remacle, F; Verstraete, Matthieu J

    2015-05-12

    Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrödinger equation based on the correlated field-free stationary electronic states computed with the equationof-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TDDFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.

  9. Advances in Computational High-Resolution Mechanical Spectroscopy HRMS Part II: Resonant Frequency – Young's Modulus

    International Nuclear Information System (INIS)

    Majewski, M; Magalas, L B

    2012-01-01

    In this paper, we compare the values of the resonant frequency f 0 of free decaying oscillations computed according to the parametric OMI method (Optimization in Multiple Intervals) and nonparametric DFT-based (discrete Fourier transform) methods as a function of the sampling frequency. The analysis is carried out for free decaying signals embedded in an experimental noise recorded for metallic samples in a low-frequency resonant mechanical spectrometer. The Yoshida method (Y), the Agrez' method (A), and new interpolated discrete Fourier transform (IpDFT) methods, that is, the Yoshida-Magalas (YM) and (YM C ) methods developed by the authors are carefully compared for the resonant frequency f 0 = 1.12345 Hz and the logarithmic decrement, δ = 0.0005. Precise estimation of the resonant frequency (Youngs' modulus ∼ f 0 2 ) for real experimental conditions, i.e., for exponentially damped harmonic signals embedded in an experimental noise, is a complex task. In this work, various computing methods are analyzed as a function of the sampling frequency used to digitize free decaying oscillations. The importance of computing techniques to obtain reliable and precise values of the resonant frequency (i.e. Young's modulus) in materials science is emphasized.

  10. On the potential of zero-tail DFT-spread-OFDM in 5G networks

    DEFF Research Database (Denmark)

    Berardinelli, Gilberto; Tavares, Fernando Menezes Leitão; Sørensen, Troels Bundgaard

    2014-01-01

    Zero-tail Discrete Fourier Transform -spread OFDM (ZT DFT-s-OFDM) modulation allows to dynamically cope with the delay spread of the multipath channel, thus avoiding the limitations of hard-coded Cyclic Prefix (CP). In this paper, we discuss the potential of ZT DFT-s-OFDM modulation for the envis......, possibility of adopting unified radio numerology among different cells, reduced latency and support of agile link direction switching. The robustness of ZT DFT-s-OFDM towards non-idealities such as phase noise and non-linear power amplifier is also discussed....

  11. ZIVIS: A City Computing Platform Based on Volunteer Computing

    International Nuclear Information System (INIS)

    Antoli, B.; Castejon, F.; Giner, A.; Losilla, G.; Reynolds, J. M.; Rivero, A.; Sangiao, S.; Serrano, F.; Tarancon, A.; Valles, R.; Velasco, J. L.

    2007-01-01

    Abstract Volunteer computing has come up as a new form of distributed computing. Unlike other computing paradigms like Grids, which use to be based on complex architectures, volunteer computing has demonstrated a great ability to integrate dispersed, heterogeneous computing resources with ease. This article presents ZIVIS, a project which aims to deploy a city-wide computing platform in Zaragoza (Spain). ZIVIS is based on BOINC (Berkeley Open Infrastructure for Network Computing), a popular open source framework to deploy volunteer and desktop grid computing systems. A scientific code which simulates the trajectories of particles moving inside a stellarator fusion device, has been chosen as the pilot application of the project. In this paper we describe the approach followed to port the code to the BOINC framework as well as some novel techniques, based on standard Grid protocols, we have used to access the output data present in the BOINC server from a remote visualizer. (Author)

  12. Study on structure, vibrational analysis and molecular characteristics of some halogen substituted azido-phenylethanones using FTIR spectra and DFT

    Science.gov (United States)

    Prashanth, J.; Reddy, Byru Venkatram

    2018-03-01

    The Fourier transform infrared (FTIR) spectra of organic compounds 4-fluoro-2-azido-1-phenylethanone (FAP), 4-chloro-2-azido-1-phenylethanone (CAP) and 4-bromo-2-azido-1-phenylethanone (BAP) have been recorded in the region 4000-400 cm-1. The optimized molecular structure for global minimum energy of the titled molecules is determined by evaluating torsional potentials as a function of rotation angle about free rotation bonds among the substituent groups subjecting them to DFT employing B3LYP functional with 6-311++G (d,p) basis set. The vibrational frequencies along with infrared intensities are computed by SQM procedure. The rms error between observed and calculated frequencies is found to be 9.27, 8.17 and 7.95 cm-1 for FAP, CAP and BAP, respectively which shows good agreement between experimental and scaled values of calculated frequencies obtained by DFT. The vibrational assignments of all the fundamental bands of each molecule are made unambiguously using PED and eigen vectors obtained in the computations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the titled molecules exhibit NLO behaviour and hence may be considered for potential applicants for the development of NLO materials. HOMO and LUMO energies evaluated in the study demonstrate chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyper conjugative interactions and charge delocalization. The molecular electrostatic surface potential (MESP) and thermodynamic parameters are also evaluated.

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

    Science.gov (United States)

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

    2013-03-01

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

  14. 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.

  15. 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.

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

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Frimand, Kenneth

    2002-01-01

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

  17. 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 ...

  18. 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.

  19. DFT description of the magnetic properties and electron localization in dinuclear di-mu-oxo-bridged manganese complexes.

    Science.gov (United States)

    Barone, Vincenzo; Bencini, Alessandro; Gatteschi, Dante; Totti, Federico

    2002-11-04

    Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed.

  20. Kaxiras’s Porphyrin: DFT Modeling of Redox-Tuned Optical and Electronic Properties in a Theoretically Designed Catechol-Based Bioinspired Platform

    Directory of Open Access Journals (Sweden)

    Orlando Crescenzi

    2017-11-01

    Full Text Available A detailed computational investigation of the 5,6-dihydroxyindole (DHI-based porphyrin-type tetramer first described by Kaxiras as a theoretical structural model for eumelanin biopolymers is reported herein, with a view to predicting the technological potential of this unique bioinspired tetracatechol system. All possible tautomers/conformers, as well as alternative protonation states, were explored for the species at various degrees of oxidation and all structures were geometry optimized at the density functional theory (DFT level. Comparison of energy levels for each oxidized species indicated a marked instability of most oxidation states except the six-electron level, and an unexpected resilience to disproportionation of the one-electron oxidation free radical species. Changes in the highest energy occupied molecular orbital (HOMO–lowest energy unoccupied molecular orbital (LUMO gaps with oxidation state and tautomerism were determined along with the main electronic transitions: more or less intense absorption in the visible region is predicted for most oxidized species. Data indicated that the peculiar symmetry of the oxygenation pattern pertaining to the four catechol/quinone/quinone methide moieties, in concert with the NH centers, fine-tunes the optical and electronic properties of the porphyrin system. For several oxidation levels, conjugated systems extending over two or more indole units play a major role in determining the preferred tautomeric state: thus, the highest stability of the six-electron oxidation state reflects porphyrin-type aromaticity. These results provide new clues for the design of innovative bioinspired optoelectronic materials.

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

    Directory of Open Access Journals (Sweden)

    Yusuf Sert

    2016-01-01

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

  2. Fischer-Tropsch Synthesis on Multicomponent Catalysts: What Can We Learn from Computer Simulations?

    OpenAIRE

    Fajin, Jose L. C.; Cordeiro, M. Natalia D. S.; Gomes, Jose R. B.

    2015-01-01

    In this concise review paper, we will address recent studies based on the generalized-gradient approximation (GGA) of the density functional theory (DFT) and on the periodic slab approach devoted to the understanding of the Fischer-Tropsch synthesis process on transition metal catalysts. As it will be seen, this computational combination arises as a very adequate strategy for the study of the reaction mechanisms on transition metal surfaces under well-controlled conditions and allows separati...

  3. Acid-base properties of the N3 ruthenium(II) solar cell sensitizer: a combined experimental and computational analysis.

    Science.gov (United States)

    Pizzoli, Giuliano; Lobello, Maria Grazia; Carlotti, Benedetta; Elisei, Fausto; Nazeeruddin, Mohammad K; Vitillaro, Giuseppe; De Angelis, Filippo

    2012-10-14

    We report a combined spectro-photometric and computational investigation of the acid-base equilibria of the N3 solar cell sensitizer [Ru(dcbpyH(2))(2)(NCS)(2)] (dcbpyH(2) = 4,4'-dicarboxyl-2,2' bipyridine) in aqueous/ethanol solutions. The absorption spectra of N3 recorded at various pH values were analyzed by Single Value Decomposition techniques, followed by Global Fitting procedures, allowing us to identify four separate acid-base equilibria and their corresponding ground state pK(a) values. DFT/TDDFT calculations were performed for the N3 dye in solution, investigating the possible relevant species obtained by sequential deprotonation of the four dye carboxylic groups. TDDFT excited state calculations provided UV-vis absorption spectra which nicely agree with the experimental spectral shapes at various pH values. The calculated pK(a) values are also in good agreement with experimental data, within <1 pK(a) unit. Based on the calculated energy differences a tentative assignment of the N3 deprotonation pathway is reported.

  4. 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.

  5. Advanced computer-based training

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, H D; Martin, H D

    1987-05-01

    The paper presents new techniques of computer-based training for personnel of nuclear power plants. Training on full-scope simulators is further increased by use of dedicated computer-based equipment. An interactive communication system runs on a personal computer linked to a video disc; a part-task simulator runs on 32 bit process computers and shows two versions: as functional trainer or as on-line predictor with an interactive learning system (OPAL), which may be well-tailored to a specific nuclear power plant. The common goal of both develoments is the optimization of the cost-benefit ratio for training and equipment.

  6. Advanced computer-based training

    International Nuclear Information System (INIS)

    Fischer, H.D.; Martin, H.D.

    1987-01-01

    The paper presents new techniques of computer-based training for personnel of nuclear power plants. Training on full-scope simulators is further increased by use of dedicated computer-based equipment. An interactive communication system runs on a personal computer linked to a video disc; a part-task simulator runs on 32 bit process computers and shows two versions: as functional trainer or as on-line predictor with an interactive learning system (OPAL), which may be well-tailored to a specific nuclear power plant. The common goal of both develoments is the optimization of the cost-benefit ratio for training and equipment. (orig.) [de

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. N,N′-Dipyridoxyl(1,8-diamino-3,6-dioxaoctane) Schiff-base

    African Journals Online (AJOL)

    The N,N′-dipyridoxyl(1,8-diamino-3,6-dioxaoctane) (=H2L) Schiff-base has been synthesized and characterized by IR, 1H NMR, mass spectrometry and elemental analysis. Its optimized geometry and theoretical vibrational frequencies have been computed using density functional theory (DFT) method via the B3LYP ...

  14. An analytical study of the improved nonlinear tolerance of DFT-spread OFDM and its unitary-spread OFDM generalization.

    Science.gov (United States)

    Shulkind, Gal; Nazarathy, Moshe

    2012-11-05

    DFT-spread (DFT-S) coherent optical OFDM was numerically and experimentally shown to provide improved nonlinear tolerance over an optically amplified dispersion uncompensated fiber link, relative to both conventional coherent OFDM and single-carrier transmission. Here we provide an analytic model rigorously accounting for this numerical result and precisely predicting the optimal bandwidth per DFT-S sub-band (or equivalently the optimal number of sub-bands per optical channel) required in order to maximize the link non-linear tolerance (NLT). The NLT advantage of DFT-S OFDM is traced to the particular statistical dependency introduced among the OFDM sub-carriers by means of the DFT spreading operation. We further extend DFT-S to a unitary-spread generalized modulation format which includes as special cases the DFT-S scheme as well as a new format which we refer to as wavelet-spread (WAV-S) OFDM, replacing the spreading DFTs by Hadamard matrices which have elements +/-1 hence are multiplier-free. The extra complexity incurred in the spreading operation is almost negligible, however the performance improvement with WAV-S relative to plain OFDM is more modest than that achieved by DFT-S, which remains the preferred format for nonlinear tolerance improvement, outperforming both plain OFDM and single-carrier schemes.

  15. Computer-based multi-channel analyzer based on internet

    International Nuclear Information System (INIS)

    Zhou Xinzhi; Ning Jiaoxian

    2001-01-01

    Combined the technology of Internet with computer-based multi-channel analyzer, a new kind of computer-based multi-channel analyzer system which is based on browser is presented. Its framework and principle as well as its implementation are discussed

  16. 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...

  17. Solvent effect on indocyanine dyes: A computational approach

    International Nuclear Information System (INIS)

    Bertolino, Chiara A.; Ferrari, Anna M.; Barolo, Claudia; Viscardi, Guido; Caputo, Giuseppe; Coluccia, Salvatore

    2006-01-01

    The solvatochromic behaviour of a series of indocyanine dyes (Dyes I-VIII) was investigated by quantum chemical calculations. The effect of the polymethine chain length and of the indolenine structure has been satisfactorily reproduced by semiempirical Pariser-Parr-Pople (PPP) calculations. The solvatochromism of 3,3,3',3'-tetramethyl-N,N'-diethylindocarbocyanine iodide (Dye I) has been deeply investigated within the ab initio time-dependent density functional theory (TD-DFT) approach. Dye I undergoes non-polar solvation and a linear correlation has been individuated between absorption shifts and refractive index. Computed absorption λ max and oscillator strengths obtained by TD-DFT are in good agreement with the experimental data

  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. 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).

  20. Experimental demonstration of improved fiber nonlinearity tolerance for unique-word DFT-spread OFDM systems.

    Science.gov (United States)

    Chen, Xi; Li, An; Gao, Guanjun; Shieh, William

    2011-12-19

    In this paper we experimentally demonstrate transmission performance of optical DFT-spread OFDM systems in comparison with conventional OFDM systems. A 440.8-Gb/s superchannel consisting of 8 x 55.1-Gb/s densely-spaced DFT-S OFDM signal is successfully received after 1120-km transmission with a spectral efficiency of 3.5 b/s/Hz. It is shown that DFT-S OFDM can achieve an improvement of 1 dB in Q factor and 1 dB in launch power over conventional OFDM. Additionally, unique word aided phase estimation algorithm is proposed and demonstrated enabling extremely long OFDM symbol transmission.

  1. Critical Assessment of TD-DFT for Excited States of Open-Shell Systems: I. Doublet-Doublet Transitions.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian

    2016-01-12

    A benchmark set of 11 small radicals is set up to assess the performance of time-dependent density functional theory (TD-DFT) for the excited states of open-shell systems. Both the unrestricted (U-TD-DFT) and spin-adapted (X-TD-DFT) formulations of TD-DFT are considered. For comparison, the well-established EOM-CCSD (equation-of-motion coupled-cluster with singles and doubles) is also used. In total, 111 low-lying singly excited doublet states are accessed by all the three approaches. Taking the MRCISD+Q (multireference configuration interaction with singles and doubles plus the Davidson correction) results as the benchmark, it is found that both U-TD-DFT and EOM-CCSD perform well for those states dominated by singlet-coupled single excitations (SCSE) from closed-shell to open-shell, open-shell to vacant-shell, or closed-shell to vacant-shell orbitals. However, for those states dominated by triplet-coupled single excitations (TCSE) from closed-shell to vacant-shell orbitals, both U-TD-DFT and EOM-CCSD fail miserably due to severe spin contaminations. In contrast, X-TD-DFT provides balanced descriptions of both SCSE and TCSE. As far as the functional dependence is concerned, it is found that, when the Hartree-Fock ground state does not suffer from the instability problem, both global hybrid (GH) and range-separated hybrid (RSH) functionals perform grossly better than pure density functionals, especially for Rydberg and charge-transfer excitations. However, if the Hartree-Fock ground state is instable or nearly instable, GH and RSH tend to underestimate severely the excitation energies. The SAOP (statistically averaging of model orbital potentials) performs more uniformly than any other density functionals, although it generally overestimates the excitation energies of valence excitations. Not surprisingly, both EOM-CCSD and adiabatic TD-DFT are incapable of describing excited states with substantial double excitation characters.

  2. Demostration of 520 Gb/s/λ pre-equalized DFT-spread PDM-16QAM-OFDM signal transmission.

    Science.gov (United States)

    Li, Fan; Yu, Jianjun; Cao, Zizheng; Chen, Ming; Zhang, Junwen; Li, Xinying

    2016-02-08

    In this paper, we successfully transmit 8 × 520 Gb/s pre-equalized DFT-spread PDM-16QAM orthogonal frequency-division multiplexing (OFDM) signal over 840 km SMF with BER under 2.4 × 10(-2). We discuss how to obtain accurate tranceivers' response during pre-equalization for DFT-spread OFDM with coherent detection and we find conventional OFDM symbols training sequences (TSs) outperform DFT-spread OFDM symbols TSs in obtaining channel response for pre-equalization and equalization. Additionally, the optimal IFFT/FFT size is explored for the pre-equalized DFT-spread PDM-16QAM-OFDM transmission systems. It is the first time to realize 400 Gb/s/λ net rate OFDM signal transmission.

  3. 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

  4. 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)

  5. 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.

  6. Shock compression of glow discharge polymer (GDP): density functional theory (DFT) simulations and experiments on Sandia's Z-machine

    Science.gov (United States)

    Mattsson, Thomas R.; Cochrane, K. R.; Ao, T.; Lemke, R. W.; Flicker, D. G.; Schoff, M. E.; Blue, B. E.; Hamel, S.; Herrmann, M. C.

    2015-11-01

    Glow discharge polymer (GDP) is used extensively as capsule/ablation material in inertial confinement fusion (ICF) capsules. Accurate knowledge of the equation of state (EOS) under shock and release is particularly important for high-fidelity design, analysis, and optimization of ICF experiments since the capsule material is subject to several converging shocks as well as release towards the cryogenic fuel. We performed Density Functional Theory (DFT) based quantum molecular dynamics (QMD) simulations, to gain knowledge of the behavior of GDP - including the effect of changes in chemical composition. The shock pressures calculated from DFT are compared experimental data taken on magnetically launched flyer plate impact experiments on at Sandia's Z-machine. Large GDP samples were grown in a planar geometry to improve the sample quality and maintained in a nitrogen atmosphere following manufacturing, thus allowing for a direct comparison to the DFT/QMD simulations. 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 NNSA under contract DE-AC04-94AL85000.

  7. Cysteine protease inhibition by nitrile-based inhibitors: a computational study

    Science.gov (United States)

    Quesne, Matthew G.; Ward, Richard A.; de Visser, Sam P.

    2013-01-01

    Cysteine protease enzymes are important for human physiology and catalyze key protein degradation pathways. These enzymes react via a nucleophilic reaction mechanism that involves a cysteine residue and the proton of a proximal histidine. Particularly efficient inhibitors of these enzymes are nitrile-based, however, the details of the catalytic reaction mechanism currently are poorly understood. To gain further insight into the inhibition of these molecules, we have performed a combined density functional theory and quantum mechanics/molecular mechanics study on the reaction of a nitrile-based inhibitor with the enzyme active site amino acids. We show here that small perturbations to the inhibitor structure can have dramatic effects on the catalysis and inhibition processes. Thus, we investigated a range of inhibitor templates and show that specific structural changes reduce the inhibitory efficiency by several orders of magnitude. Moreover, as the reaction takes place on a polar surface, we find strong differences between the DFT and QM/MM calculated energetics. In particular, the DFT model led to dramatic distortions from the starting structure and the convergence to a structure that would not fit the enzyme active site. In the subsequent QM/MM study we investigated the use of mechanical vs. electronic embedding on the kinetics, thermodynamics and geometries along the reaction mechanism. We find minor effects on the kinetics of the reaction but large geometric and thermodynamics differences as a result of inclusion of electronic embedding corrections. The work here highlights the importance of model choice in the investigation of this biochemical reaction mechanism. PMID:24790966

  8. Understanding reactivity of two newly synthetized imidazole derivatives by spectroscopic characterization and computational study

    Science.gov (United States)

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

    2018-04-01

    Two newly synthetized imidazole derivatives (1-(4-methoxyphenyl)-4,5-dimethyl-1H-imidazole-2-yl acetate (MPDIA) and 1-(4-bromophenyl)-4,5-dimethyl-1H-imidazole-2-yl acetate (BPDIA)) have been prepared by solvent-free synthesis pathway and their specific spectroscopic and reactive properties have been discussed based on combined experimental and computational approaches. Aside of synthesis, experimental part of this work included measurements of IR, FT-Raman and NMR spectra. All of the aforementioned spectra were also obtained computationally, within the framework of density functional theory (DFT) approach. Additionally, DFT calculations have been used in order to investigate local reactivity properties based on molecular orbital theory, molecular electrostatic potential (MEP), average local ionization energy (ALIE), Fukui functions and bond dissociation energy (BDE). Molecular dynamics (MD) simulations have been used in order to obtain radial distribution functions (RDF), which were used for identification of the atoms with pronounced interactions with water molecules. MEP showed negative regions are mainly localized over N28, O29, O35 atoms, it is represent with red colour in rainbow color scheme for MPDIA and BPDIA (which are most reactive sites for electrophilic attack). The first order hyperpolarizabilities of MPDIA and BPDIA are 20.15 and 6.10 times that of the standard NLO material urea. Potential interaction with antihypertensive protein hydrolase.

  9. 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; ...

  10. 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.

  11. Mechanical and magneto-opto-electronic investigation of transition metal based fluoro-perovskites: An ab-initio DFT study

    Science.gov (United States)

    Erum, Nazia; Azhar Iqbal, Muhammad

    2017-09-01

    Detailed ab-initio calculations are performed to investigate structural, elastic, mechanical, magneto-electronic and optical properties of the KXF3 (X = V, Fe, Co, Ni) fluoro-perovskites using Full Potential Linearized Augmented Plane Wave (FP-LAPW) method within the framework of density functional theory (DFT). The calculated structural parameters by DFT and analytical methods are found consistent with the experimental results. From the elastic and mechanical properties, it can be inferred that these compounds are elastically stable and anisotropic while KCoF3 is harder than rest of the compounds. Furthermore, thermal behavior of these compounds is analyzed by calculating Debye temperature (θD). The calculated spin dependent magneto-electronic properties in these compounds reveal that exchange splitting is dominated by N-3d orbital. The stable magnetic phase optimizations verify the experimental observations at low temperature. Type of chemical bonding is analyzed with the help of variations in electron density difference distribution that is induced due to changes of the second cation. The linear optical properties are also discussed in terms of optical spectra. The present methodology represents an influential approach to calculate the whole set of mechanical and magneto-opto-electronic parameters, which would support to understand various physical phenomena and empower device engineers for implementing these materials in spintronic applications.

  12. Application of DFT Filter Banks and Cosine Modulated Filter Banks in Filtering

    Science.gov (United States)

    Lin, Yuan-Pei; Vaidyanathan, P. P.

    1994-01-01

    None given. This is a proposal for a paper to be presented at APCCAS '94 in Taipei, Taiwan. (From outline): This work is organized as follows: Sec. II is devoted to the construction of the new 2m channel under-decimated DFT filter bank. Implementation and complexity of this DFT filter bank are discussed therein. IN a similar manner, the new 2m channel cosine modulated filter bank is discussed in Sec. III. Design examples are given in Sec. IV.

  13. Knowledge-based computer security advisor

    International Nuclear Information System (INIS)

    Hunteman, W.J.; Squire, M.B.

    1991-01-01

    The rapid expansion of computer security information and technology has included little support to help the security officer identify the safeguards needed to comply with a policy and to secure a computing system. This paper reports that Los Alamos is developing a knowledge-based computer security system to provide expert knowledge to the security officer. This system includes a model for expressing the complex requirements in computer security policy statements. The model is part of an expert system that allows a security officer to describe a computer system and then determine compliance with the policy. The model contains a generic representation that contains network relationships among the policy concepts to support inferencing based on information represented in the generic policy description

  14. 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.

  15. A study of vibrational spectra and investigations of charge transfer and chemical bonding features of 2-chloro benzimidazole based on DFT computations

    Science.gov (United States)

    Muthunatesan, S.; Ragavendran, V.

    2015-01-01

    Benzimidazoles are bicyclic heteroatomic molecules. Polycyclic heteroatomic molecules have extensive coupling of different modes leading to strong coupling of force constants associated with the various chemical bonds of the molecules. To carry out a detailed vibrational spectroscopic analysis of such a bicyclic heteroatomic molecule, FT-IR and FT-Raman spectra of 2-chloro benzimidazole (CBZ) have been recorded in the condensed phase. Density Functional Theory calculations in the B3LYP/6-31G* level have been carried out to determine the optimized geometry and vibrational frequencies. In order to obtain a close agreement between theoretical and observed frequencies and hence to perform a reliable assignment, the theoretical DFT force field was transformed from Cartesian to local symmetry co-ordinates and then scaled empirically using SQM methodology. The SQM treatment resulted in a RMS deviation of 9.4 cm-1. For visual comparison, the observed and calculated spectra are presented on a common wavenumber scale. From the NBO analysis, the electron density (ED) charge transfers in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated Homo and Lumo energies show that charge transfer occurs within the molecule. The results obtained from the vibrational, NBO and HOMO-LUMO analyses have been properly tabulated.

  16. Organic electronic materials: Recent advances in the dft description of the ground and excited states using tuned range-separated hybrid functionals

    KAUST Repository

    Körzdörfer, Thomas

    2014-11-18

    Density functional theory (DFT) and its time-dependent extension (TD-DFT) are powerful tools enabling the theoretical prediction of the ground- and excited-state properties of organic electronic materials with reasonable accuracy at affordable computational costs. Due to their excellent accuracy-to-numerical-costs ratio, semilocal and global hybrid functionals such as B3LYP have become the workhorse for geometry optimizations and the prediction of vibrational spectra in modern theoretical organic chemistry. Despite the overwhelming success of these out-of-the-box functionals for such applications, the computational treatment of electronic and structural properties that are of particular interest in organic electronic materials sometimes reveals severe and qualitative failures of such functionals. Important examples include the overestimation of conjugation, torsional barriers, and electronic coupling as well as the underestimation of bond-length alternations or excited-state energies in low-band-gap polymers.In this Account, we highlight how these failures can be traced back to the delocalization error inherent to semilocal and global hybrid functionals, which leads to the spurious delocalization of electron densities and an overestimation of conjugation. The delocalization error for systems and functionals of interest can be quantified by allowing for fractional occupation of the highest occupied molecular orbital. It can be minimized by using long-range corrected hybrid functionals and a nonempirical tuning procedure for the range-separation parameter.We then review the benefits and drawbacks of using tuned long-range corrected hybrid functionals for the description of the ground and excited states of π-conjugated systems. In particular, we show that this approach provides for robust and efficient means of characterizing the electronic couplings in organic mixed-valence systems, for the calculation of accurate torsional barriers at the polymer limit, and for the

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

    Science.gov (United States)

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

    2014-08-14

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

  18. Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT and Time-Dependent Density Functional Theory (TD-DFT Study

    Directory of Open Access Journals (Sweden)

    Guo-Jun Kang

    2016-11-01

    Full Text Available The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH3-YD2 and TPhe-YD were systematically investigated by density functional theory (DFT and time-dependent density functional theory (TD-DFT to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO2 cluster were fully investigated. From the analyses of natural bond orbital (NBO, extended charge decomposition analysis (ECDA, and electron density variations (Δρ between the excited state and ground state, it was found that the introduction of N(CH32 and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH32 and 1,1,2-triphenylethene groups. NCH3-YD2 with N(CH32 groups in the donor part is an effective way to improve the interactions between the dyes and TiO2 surface, light having efficiency (LHE, and free energy change (ΔGinject, which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs.

  19. Unified commutation-pruning technique for efficient computation of composite DFTs

    Science.gov (United States)

    Castro-Palazuelos, David E.; Medina-Melendrez, Modesto Gpe.; Torres-Roman, Deni L.; Shkvarko, Yuriy V.

    2015-12-01

    An efficient computation of a composite length discrete Fourier transform (DFT), as well as a fast Fourier transform (FFT) of both time and space data sequences in uncertain (non-sparse or sparse) computational scenarios, requires specific processing algorithms. Traditional algorithms typically employ some pruning methods without any commutations, which prevents them from attaining the potential computational efficiency. In this paper, we propose an alternative unified approach with automatic commutations between three computational modalities aimed at efficient computations of the pruned DFTs adapted for variable composite lengths of the non-sparse input-output data. The first modality is an implementation of the direct computation of a composite length DFT, the second one employs the second-order recursive filtering method, and the third one performs the new pruned decomposed transform. The pruned decomposed transform algorithm performs the decimation in time or space (DIT) data acquisition domain and, then, decimation in frequency (DIF). The unified combination of these three algorithms is addressed as the DFTCOMM technique. Based on the treatment of the combinational-type hypotheses testing optimization problem of preferable allocations between all feasible commuting-pruning modalities, we have found the global optimal solution to the pruning problem that always requires a fewer or, at most, the same number of arithmetic operations than other feasible modalities. The DFTCOMM method outperforms the existing competing pruning techniques in the sense of attainable savings in the number of required arithmetic operations. It requires fewer or at most the same number of arithmetic operations for its execution than any other of the competing pruning methods reported in the literature. Finally, we provide the comparison of the DFTCOMM with the recently developed sparse fast Fourier transform (SFFT) algorithmic family. We feature that, in the sensing scenarios with

  20. Identity-Based Authentication for Cloud Computing

    Science.gov (United States)

    Li, Hongwei; Dai, Yuanshun; Tian, Ling; Yang, Haomiao

    Cloud computing is a recently developed new technology for complex systems with massive-scale services sharing among numerous users. Therefore, authentication of both users and services is a significant issue for the trust and security of the cloud computing. SSL Authentication Protocol (SAP), once applied in cloud computing, will become so complicated that users will undergo a heavily loaded point both in computation and communication. This paper, based on the identity-based hierarchical model for cloud computing (IBHMCC) and its corresponding encryption and signature schemes, presented a new identity-based authentication protocol for cloud computing and services. Through simulation testing, it is shown that the authentication protocol is more lightweight and efficient than SAP, specially the more lightweight user side. Such merit of our model with great scalability is very suited to the massive-scale cloud.

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

    Science.gov (United States)

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

    2014-07-01

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

  2. 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)

  3. Shock compression of glow discharge polymer (GDP): density functional theory (DFT) simulations and experiments on Sandia's Z machine

    Science.gov (United States)

    Cochrane, Kyle R.; Ao, T.; Lemke, R. W.; Hamel, S.; Schoff, M. E.; Blue, B. E.; Herrmann, M. C.; Mattsson, T. R.

    2014-03-01

    Glow discharge polymer (GDP) is used extensively as capsule/ablation material in inertial confinement fusion (ICF) capsules. Accurate knowledge of the equation of state (EOS) under shock and release is particularly important for high-fidelity design, analysis, and optimization of ICF experiments since the capsule material is subject to several converging shocks as well as release towards the cryogenic fuel. We performed Density Functional Theory (DFT) based quantum molecular dynamics (QMD) simulations, to gain knowledge of the behavior of GDP - for example regarding the role of chemical dissociation during shock compression, we find that the dissociation regime along the Hugoniot extends from 50 GPa to 250 GPa. The shock pressures calculated from DFT are compared experimental data taken at Sandia's Z-machine. The GDP samples were grown in a planar geometry to improve the sample quality and maintained in a nitrogen atmosphere following manufacturing, thus allowing for a direct comparison to the DFT/QMD simulations. 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 NNSA under contract DE-AC04-94AL85000.

  4. Spintronics-based computing

    CERN Document Server

    Prenat, Guillaume

    2015-01-01

    This book provides a comprehensive introduction to spintronics-based computing for the next generation of ultra-low power/highly reliable logic, which is widely considered a promising candidate to replace conventional, pure CMOS-based logic. It will cover aspects from device to system-level, including magnetic memory cells, device modeling, hybrid circuit structure, design methodology, CAD tools, and technological integration methods. This book is accessible to a variety of readers and little or no background in magnetism and spin electronics are required to understand its content.  The multidisciplinary team of expert authors from circuits, devices, computer architecture, CAD and system design reveal to readers the potential of spintronics nanodevices to reduce power consumption, improve reliability and enable new functionality.  .

  5. Comprehensive Characterization of Palygorskite from Torrejon el Rubio (Spain) Based on Experimental Techniques and Theoretical DFT Studies

    International Nuclear Information System (INIS)

    Fernandez, A.M.; Timon, V.; Cubero, J. J.; Sanchez-Ledesma, D. M.; Gutierrez-Nebot, L.; Martinez, J. J.; Romero, C.; Labajo, M.; Melon, A.; Barrios, I.

    2013-01-01

    New data about the physico-chemical, microstructural and crystal-chemical properties of the mineral paligorskite from Torrejon el Rubio (Caceres, Spain) were obtained by a combination of experimental techniques (XRD, FRX, FTIR, TG-DSC, SEM and chemical analyses), as well as geometry optimization by means of the Density Functional Theory (DFT). This study demonstrates the applicability of the mixed theoretical-experimental work to characterize and understand the properties of clay minerals used in technological applications and environmental remediation. (Author)

  6. Comprehensive Characterization of Palygorskite from Torrejon el Rubio (Spain) Based on Experimental Techniques and Theoretical DFT Studies

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, A.M.; Timon, V.; Cubero, J. J.; Sanchez-Ledesma, D. M.; Gutierrez-Nebot, L.; Martinez, J. J.; Romero, C.; Labajo, M.; Melon, A.; Barrios, I.

    2013-10-01

    New data about the physico-chemical, microstructural and crystal-chemical properties of the mineral paligorskite from Torrejon el Rubio (Caceres, Spain) were obtained by a combination of experimental techniques (XRD, FRX, FTIR, TG-DSC, SEM and chemical analyses), as well as geometry optimization by means of the Density Functional Theory (DFT). This study demonstrates the applicability of the mixed theoretical-experimental work to characterize and understand the properties of clay minerals used in technological applications and environmental remediation. (Author)

  7. A Computer-Based Simulation of an Acid-Base Titration

    Science.gov (United States)

    Boblick, John M.

    1971-01-01

    Reviews the advantages of computer simulated environments for experiments, referring in particular to acid-base titrations. Includes pre-lab instructions and a sample computer printout of a student's use of an acid-base simulation. Ten references. (PR)

  8. 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

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

    Science.gov (United States)

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

    2018-05-01

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

  10. Predicting Structures of Ru-Centered Dyes: A Computational Screening Tool.

    Science.gov (United States)

    Fredin, Lisa A; Allison, Thomas C

    2016-04-07

    Dye-sensitized solar cells (DSCs) represent a means for harvesting solar energy to produce electrical power. Though a number of light harvesting dyes are in use, the search continues for more efficient and effective compounds to make commercially viable DSCs a reality. Computational methods have been increasingly applied to understand the dyes currently in use and to aid in the search for improved light harvesting compounds. Semiempirical quantum chemistry methods have a well-deserved reputation for giving good quality results in a very short amount of computer time. The most recent semiempirical models such as PM6 and PM7 are parametrized for a wide variety of molecule types, including organometallic complexes similar to DSC chromophores. In this article, the performance of PM6 is tested against a set of 20 molecules whose geometries were optimized using a density functional theory (DFT) method. It is found that PM6 gives geometries that are in good agreement with the optimized DFT structures. In order to reduce the differences between geometries optimized using PM6 and geometries optimized using DFT, the PM6 basis set parameters have been optimized for a subset of the molecules. It is found that it is sufficient to optimize the basis set for Ru alone to improve the agreement between the PM6 results and the DFT results. When this optimized Ru basis set is used, the mean unsigned error in Ru-ligand bond lengths is reduced from 0.043 to 0.017 Å in the set of 20 test molecules. Though the magnitude of these differences is small, the effect on the calculated UV/vis spectra is significant. These results clearly demonstrate the value of using PM6 to screen DSC chromophores as well as the value of optimizing PM6 basis set parameters for a specific set of molecules.

  11. From the X-rays to a reliable “low cost” computational structure of caffeic acid: DFT, MP2, HF and integrated molecular dynamics-X-ray diffraction approach to condensed phases

    Science.gov (United States)

    Lombardo, Giuseppe M.; Portalone, Gustavo; Colapietro, Marcello; Rescifina, Antonio; Punzo, Francesco

    2011-05-01

    The ability of caffeic acid to act as antioxidant against hyperoxo-radicals as well as its recently found therapeutic properties in the treatment of hepatocarcinoma, still make this compound, more than 20 years later the refinement of its crystal structure, object of study. It belongs to the vast family of humic substances, which play a key role in the biodegradation processes and easily form complexes with ions widely diffused in the environment. This class of compounds is therefore interesting for potential environmental chemistry applications concerning the possible complexation of heavy metals. Our study focused on the characterization of caffeic acid as a starting necessary step, which will be followed in the future by the application of our findings on the study of the properties of caffeate anion interaction with heavy metal ions. To reach this goal, we applied a low cost approach - in terms of computational time and resources - aimed at the achievement of a high resolution, robust and trustable structure using the X-ray single crystal data, recollected with a higher resolution, as touchstone for a detailed check. A comparison between the calculations carried out with density functional theory (DFT), Hartree-Fock (HF) method and post SCF second order Møller-Plesset perturbation method (MP2), at the 6-31G ** level of the theory, molecular mechanics (MM) and molecular dynamics (MD) was performed. As a consequence we explained on one hand the possible reasons for the pitfalls of the DFT approach and on the other the benefits of using a good and robust force field developed for condensed phases, as AMBER, with MM and MD. The reliability of the latter, highlighted by the overall agreement extended up to the anisotropic displacement parameters calculated by means of MD and the ones gathered by X-ray measurements, makes it very promising for the above-mentioned goals.

  12. Computer-based and web-based radiation safety training

    Energy Technology Data Exchange (ETDEWEB)

    Owen, C., LLNL

    1998-03-01

    The traditional approach to delivering radiation safety training has been to provide a stand-up lecture of the topic, with the possible aid of video, and to repeat the same material periodically. New approaches to meeting training requirements are needed to address the advent of flexible work hours and telecommuting, and to better accommodate individuals learning at their own pace. Computer- based and web-based radiation safety training can provide this alternative. Computer-based and web- based training is an interactive form of learning that the student controls, resulting in enhanced and focused learning at a time most often chosen by the student.

  13. Benchmarking gate-based quantum computers

    Science.gov (United States)

    Michielsen, Kristel; Nocon, Madita; Willsch, Dennis; Jin, Fengping; Lippert, Thomas; De Raedt, Hans

    2017-11-01

    With the advent of public access to small gate-based quantum processors, it becomes necessary to develop a benchmarking methodology such that independent researchers can validate the operation of these processors. We explore the usefulness of a number of simple quantum circuits as benchmarks for gate-based quantum computing devices and show that circuits performing identity operations are very simple, scalable and sensitive to gate errors and are therefore very well suited for this task. We illustrate the procedure by presenting benchmark results for the IBM Quantum Experience, a cloud-based platform for gate-based quantum computing.

  14. 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

  15. Synthesis, characterization and computational studies of (E-2-{[(2-aminopyridin-3-ylimino]-methyl}-4,6-di-tert-butylphenol

    Directory of Open Access Journals (Sweden)

    Alexander Carreño

    2014-01-01

    Full Text Available (E-2-{[(2-Aminopyridin-3-ylimino]-methyl}-4,6-di-tert-butyl-phenol ( 3: , a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, ¹H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL charge transfer.

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

    Science.gov (United States)

    Uludağ, Nesimi; Serdaroğlu, Goncagül

    2018-03-01

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

  17. An Emotional Agent Model Based on Granular Computing

    Directory of Open Access Journals (Sweden)

    Jun Hu

    2012-01-01

    Full Text Available Affective computing has a very important significance for fulfilling intelligent information processing and harmonious communication between human being and computers. A new model for emotional agent is proposed in this paper to make agent have the ability of handling emotions, based on the granular computing theory and the traditional BDI agent model. Firstly, a new emotion knowledge base based on granular computing for emotion expression is presented in the model. Secondly, a new emotional reasoning algorithm based on granular computing is proposed. Thirdly, a new emotional agent model based on granular computing is presented. Finally, based on the model, an emotional agent for patient assistant in hospital is realized, experiment results show that it is efficient to handle simple emotions.

  18. 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.

  19. 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.

  20. Density functional theory (DFT) study on the hydrolysis behavior of degradable Mg/Mg alloys for biomedical applications

    Science.gov (United States)

    Nezafati, Marjan

    Magnesium-based (Mg and/or Mg alloys) materials possess many advantageous physicochemical/biological characteristics such as good biocompatibility and similarity of the mechanical properties to the human bone tissue, which renders this material a promising candidate for the biomedical and implant applications. One of the most attractive features of Mg-based materials is the degradability in the physiological environment. With the burst of research on the biodegradable materials for the healthcare device applications, Mg and its alloys attracted a strong attention in the bioengineering field in recent years. However, the major limitation of applying Mg-based materials to biomedical applications is the fast degradation/corrosion rate with regards to the healing process time-span. In the present thesis, an atomistic model employing the density-functional theory (DFT) has been developed to study the hydrolysis process by understanding the influences of commonly used alloying elements (zinc (Zn), calcium (Ca), aluminum (Al), and yttrium (Y)) and the crystallographic orientation of the dissolution surfaces (basal (0001), prism (1010), and pyramidal (1011) planes) on the corrosion behavior. These parameters are known to strongly impact the initial hydrolysis phenomena of Mg-based materials. To develop the atomistic computational model, we have implemented the Dmol3 software package in conjunction with PBE (Perdew, Burke and Ernzerhof) correlation energy functional in the GGA (generalized gradient approximation) scheme. Throughout the thesis, we performed three sets of calculations, i) surface energy, ii) dissolution potential, and iii) water adsorption computations, to examine the hydrolysis mechanism and the subsequent corrosion/degradation of Mg/Mg alloys. The total energy changes of various Mg-based systems in different conditions for these surface energies, dissolution behavior, and tendency of the system for adsorbing the water molecule were quantified. The results

  1. Oxidized graphene as an electrode material for rechargeable metal-ion batteries – a DFT point of view

    International Nuclear Information System (INIS)

    Dobrota, Ana S.; Pašti, Igor A.; Skorodumova, Natalia V.

    2015-01-01

    Graphical abstract: - Abstract: In line with a growing interest in the use of graphene-based materials for energy storage applications and active research in the field of rechargeable metal-ion batteries we have performed a DFT based computational study of alkali metal atoms (Li, Na and K) interaction with an oxidized graphene. The presence of oxygen surface groups (epoxy and hydroxyl) alters the chemisorption properties of graphene. In particular, we observe that the epoxy groups are redox active and enhance the alkali metal adsorption energies by a factor of 2 or more. When an alkali metal atom interacts with hydroxyl-graphene the formation of metal-hydroxide is observed. In addition to a potential boost of metal ion storage capability, oxygen functional groups also prevent the precipitation of the metal phase. By simulating lithiation/de-lithiation process on epoxy-graphenes, it was concluded that the oxidized graphene can undergo structural changes during battery operation. Our results suggest that the content and the type of oxygen surface groups should be carefully tailored to maximize the performance of metal-ion batteries. This is mainly related to the control of the oxidation level in order to provide enough active centers for metal ion storage while preserving sufficient electrical conductivity

  2. On the computation of molecular surface correlations for protein docking using fourier techniques.

    Science.gov (United States)

    Sakk, Eric

    2007-08-01

    The computation of surface correlations using a variety of molecular models has been applied to the unbound protein docking problem. Because of the computational complexity involved in examining all possible molecular orientations, the fast Fourier transform (FFT) (a fast numerical implementation of the discrete Fourier transform (DFT)) is generally applied to minimize the number of calculations. This approach is rooted in the convolution theorem which allows one to inverse transform the product of two DFTs in order to perform the correlation calculation. However, such a DFT calculation results in a cyclic or "circular" correlation which, in general, does not lead to the same result as the linear correlation desired for the docking problem. In this work, we provide computational bounds for constructing molecular models used in the molecular surface correlation problem. The derived bounds are then shown to be consistent with various intuitive guidelines previously reported in the protein docking literature. Finally, these bounds are applied to different molecular models in order to investigate their effect on the correlation calculation.

  3. 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.

  4. 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.

  5. Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and thieno[3,2-c]coumarins derivatives: structure, electronic spectra and TD-DFT study

    Science.gov (United States)

    Akchurin, Igor O.; Yakhutina, Anna I.; Bochkov, Andrei Y.; Solovjova, Natalya P.; Medvedev, Michael G.; Traven, Valerii F.

    2018-05-01

    Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and 7-(diethylamino)thieno[3,2-c]coumarins derivatives have been synthesized using formyl derivatives of furo- and thieno[3,2-c]coumarins as starting materials. Electron absorption and fluorescent spectra of the dyes have been recorded in different solvents. Structure and solvent effects on the dyes spectral characteristics were analyzed. The fusion of five-membered heterocycle to coumarin provides a definite increase of Stokes shifts in all solvents and results in higher quantum yields of fluorescence. The absorption and emission bands of thieno[3,2-c] coumarin derivatives are definitely shifted to the red region (3-30 nm) compared to similar derivatives of furo[3,2-c]coumarin. TD-DFT calculations of some of the studied compounds have shown that hybrid DFT functionals and adequate representation of molecular environment are essential for obtaining accurate UV-Vis absorption spectra for the dyes with extended π-system. The longest-wave electron transitions in the studied compounds were computationally shown to be of push-pull nature.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  7. Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridine-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

    Energy Technology Data Exchange (ETDEWEB)

    Carreno, Alexander; Vega, Andres, E-mail: ichavez@uc.cl [Departamento de Ciencias Quimicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Santiago (Chile); Zarate, Ximena; Schott, Eduardo [Lab. Bionanotecnologia, Departamento de Ciencias Quimico-Biologicas, Universidad Bernardo O' Higgins, Santiago (Chile); Gacitua, Manuel; Valenzuela, Ninnette; Manriquez, Juan M.; Chavez, Ivonne [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago (Chile); Preite, Marcelo [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago (Chile)

    2014-07-01

    (E)-2-{[(2-Aminopyridine-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, {sup 1}H-NMR, {sup 13}C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer. (author)

  8. 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 ...

  9. 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.

  10. 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.

  11. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-15

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

  13. Optical Gaps in Pristine and Heavily Doped Silicon Nanocrystals: DFT versus Quantum Monte Carlo Benchmarks.

    Science.gov (United States)

    Derian, R; Tokár, K; Somogyi, B; Gali, Á; Štich, I

    2017-12-12

    We present a time-dependent density functional theory (TDDFT) study of the optical gaps of light-emitting nanomaterials, namely, pristine and heavily B- and P-codoped silicon crystalline nanoparticles. Twenty DFT exchange-correlation functionals sampled from the best currently available inventory such as hybrids and range-separated hybrids are benchmarked against ultra-accurate quantum Monte Carlo results on small model Si nanocrystals. Overall, the range-separated hybrids are found to perform best. The quality of the DFT gaps is correlated with the deviation from Koopmans' theorem as a possible quality guide. In addition to providing a generic test of the ability of TDDFT to describe optical properties of silicon crystalline nanoparticles, the results also open up a route to benchmark-quality DFT studies of nanoparticle sizes approaching those studied experimentally.

  14. Pervasive Computing Support for Hospitals: An Overview of the Activity-Based Computing Project

    DEFF Research Database (Denmark)

    Christensen, Henrik Bærbak; Bardram, Jakob E

    2007-01-01

    The activity-based computing project researched pervasive computing support for clinical hospital work. Such technologies have potential for supporting the mobile, collaborative, and disruptive use of heterogeneous embedded devices in a hospital......The activity-based computing project researched pervasive computing support for clinical hospital work. Such technologies have potential for supporting the mobile, collaborative, and disruptive use of heterogeneous embedded devices in a hospital...

  15. Reheating breakfast: Age and multitasking on a computer-based and a non-computer-based task

    OpenAIRE

    Feinkohl, I.; Cress, U.; Kimmerle, J.

    2016-01-01

    Computer-based assessments are popular means to measure individual differences, including age differences, in cognitive ability, but are rarely tested for the extent to which they correspond to more realistic behavior. In the present study, we explored the extent to which performance on an existing computer-based task of multitasking ('cooking breakfast') may be generalizable by comparing it with a newly developed version of the same task that required interaction with physical objects. Twent...

  16. Hilbert-Twin – A Novel Hilbert Transform-Based Method To Compute Envelope Of Free Decaying Oscillations Embedded In Noise, And The Logarithmic Decrement In High-Resolution Mechanical Spectroscopy HRMS

    Directory of Open Access Journals (Sweden)

    Magalas L.B.

    2015-06-01

    Full Text Available In this work, we present a novel Hilbert-twin method to compute an envelope and the logarithmic decrement, δ, from exponentially damped time-invariant harmonic strain signals embedded in noise. The results obtained from five computing methods: (1 the parametric OMI (Optimization in Multiple Intervals method, two interpolated discrete Fourier transform-based (IpDFT methods: (2 the Yoshida-Magalas (YM method and (3 the classic Yoshida (Y method, (4 the novel Hilbert-twin (H-twin method based on the Hilbert transform, and (5 the conventional Hilbert transform (HT method are analyzed and compared. The fundamental feature of the Hilbert-twin method is the efficient elimination of intrinsic asymmetrical oscillations of the envelope, aHT (t, obtained from the discrete Hilbert transform of analyzed signals. Excellent performance in estimation of the logarithmic decrement from the Hilbert-twin method is comparable to that of the OMI and YM for the low- and high-damping levels. The Hilbert-twin method proved to be robust and effective in computing the logarithmic decrement and the resonant frequency of exponentially damped free decaying signals embedded in experimental noise. The Hilbert-twin method is also appropriate to detect nonlinearities in mechanical loss measurements of metals and alloys.

  17. Can Expanded Bacteriochlorins Act as Photosensitizers in Photodynamic Therapy? Good News from Density Functional Theory Computations

    Directory of Open Access Journals (Sweden)

    Gloria Mazzone

    2016-02-01

    Full Text Available The main photophysical properties of a series of expanded bacteriochlorins, recently synthetized, have been investigated by means of DFT and TD-DFT methods. Absorption spectra computed with different exchange-correlation functionals, B3LYP, M06 and ωB97XD, have been compared with the experimental ones. In good agreement, all the considered systems show a maximum absorption wavelength that falls in the therapeutic window (600–800 nm. The obtained singlet-triplet energy gaps are large enough to ensure the production of cytotoxic singlet molecular oxygen. The computed spin-orbit matrix elements suggest a good probability of intersystem spin-crossing between singlet and triplet excited states, since they result to be higher than those computed for 5,10,15,20-tetrakis-(m-hydroxyphenylchlorin (Foscan© already used in the photodynamic therapy (PDT protocol. Because of the investigated properties, these expanded bacteriochlorins can be proposed as PDT agents.

  18. Demonstration of DFT-spread 256QAM-OFDM signal transmission with cost-effective directly modulated laser.

    Science.gov (United States)

    Li, Fan; Yu, Jianjun; Fang, Yuan; Dong, Ze; Li, Xinying; Chen, Lin

    2014-04-07

    We experimentally demonstrated a 256-ary quadrature amplitude modulation (256QAM) direct-detection optical orthogonal frequency division multiplexing (DDO-OFDM) transmission system utilizing a cost-effective directly modulated laser (DML). Intra-symbol frequency-domain averaging (ISFA) is applied to suppress in-band noise while the channel response estimation and Discrete Fourier Transform-spread (DFT-spread) is used to reduce the peak-to-average power ratio (PAPR) of the transmitted OFDM signal. The bit-error ratio (BER) of 15-Gbit/s 256QAM-OFDM signal has been measured after 20-km SSMF transmission that is less than 7% forward-error-correction (FEC) threshold of 3.8 × 10(-3) as the launch power into fiber is set at 6dBm. For 11.85-Gbit/s 256QAM-OFDM signal, with the aid of ISFA-based channel estimation and PAPR reduction enabled by DFT-spread, the BER after 20-km SSMF transmission can be improved from 6.4 × 10(-3) to 6.8 × 10(-4) when the received optical power is -6dBm.

  19. Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT

    DEFF Research Database (Denmark)

    Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens Kehlet

    2008-01-01

    The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells but not in ac......The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells...... but not in acidic PEM fuel cells. Based on density functional theory calculations we investigate the electrochemically most stable surface structures as a function of pH and electrostatic potential for Pt(111), Ag(111) and Ni(111), and we construct surface Pourbaix diagrams. We study the oxygen reduction reaction......, on the other hand, is constant vs. the standard hydrogen electrode (SHE). For Ag, this means that where the potential for dissolution and ORR are about the same at pH = 0, Ag becomes more stable relative to RHE as pH is increased. Hence the pH dependent stability offers an explanation for the possible use...

  20. Multiconfigurational and DFT analyses of the electromeric formulation and UV-vis absorption spectra of the superoxide adduct of ferrous superoxide reductase.

    Science.gov (United States)

    Attia, Amr A A; Cioloboc, Daniela; Lupan, Alexandru; Silaghi-Dumitrescu, Radu

    2016-12-01

    The putative initial adduct of ferrous superoxide reductase (SOR) with superoxide has been alternatively formulated as ferric-peroxo or ferrous-superoxo. The ~600-nm UV-vis absorption band proposed to be assigned to this adduct (either as sole intermediate in the SOR catalytic cycle, or as one of the two intermediates) has recently been interpreted as due to a ligand-to-metal charge transfer, involving thiolate and superoxide in a ferrous complex, contrary to an alternative assignment as a predominantly cysteine thiolate-to-ferric charge transfer in a ferric-peroxo electromer. In an attempt to clarify the electromeric formulation of this adduct, we report a computational study using a multiconfigurational complete active space self-consistent field (MC-CASSCF) wave function approach as well as modelling the UV-vis absorption spectra with time-dependent density functional theory (TD-DFT). The MC-CASSCF calculations disclose a weak interaction between iron and the dioxygenic ligand and a dominant configuration with an essentially ferrous-superoxo character. The computed UV-vis absorption spectra reveal a marked dependence on the choice of density functional - both in terms of location of bands and in terms of orbital contributors. For the main band in the visible region, besides the recently reported thiolate-to-superoxide charge transfer, a more salient, and less functional-dependent, feature is a thiolate-to-ferric iron charge transfer, consistent with a ferric-peroxo electromer. By contrast, the computed UV-vis spectra of a ferric-hydroperoxo SOR model match distinctly better (and with no qualitative dependence on the DFT methodology) the 600-nm band as due to a mainly thiolate-to-ferric character - supporting the assignment of the SOR "600-nm intermediate" as a S=5/2 ferric-hydroperoxo species. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Evaluation of computer-based ultrasonic inservice inspection systems

    International Nuclear Information System (INIS)

    Harris, R.V. Jr.; Angel, L.J.; Doctor, S.R.; Park, W.R.; Schuster, G.J.; Taylor, T.T.

    1994-03-01

    This report presents the principles, practices, terminology, and technology of computer-based ultrasonic testing for inservice inspection (UT/ISI) of nuclear power plants, with extensive use of drawings, diagrams, and LTT images. The presentation is technical but assumes limited specific knowledge of ultrasonics or computers. The report is divided into 9 sections covering conventional LTT, computer-based LTT, and evaluation methodology. Conventional LTT topics include coordinate axes, scanning, instrument operation, RF and video signals, and A-, B-, and C-scans. Computer-based topics include sampling, digitization, signal analysis, image presentation, SAFI, ultrasonic holography, transducer arrays, and data interpretation. An evaluation methodology for computer-based LTT/ISI systems is presented, including questions, detailed procedures, and test block designs. Brief evaluations of several computer-based LTT/ISI systems are given; supplementary volumes will provide detailed evaluations of selected systems

  2. Performance and stability of low-cost dye-sensitized solar cell based crude and pre-concentrated anthocyanins: Combined experimental and DFT/TDDFT study

    Science.gov (United States)

    Chaiamornnugool, Phrompak; Tontapha, Sarawut; Phatchana, Ratchanee; Ratchapolthavisin, Nattawat; Kanokmedhakul, Somdej; Sang-aroon, Wichien; Amornkitbamrung, Vittaya

    2017-01-01

    The low cost DSSCs utilized by crude and pre-concentrated anthocyanins extracted from six anthocyanin-rich samples including mangosteen pericarp, roselle, red cabbage, Thai berry, black rice and blue pea were fabricated. Their photo-to-current conversion efficiencies and stability were examined. Pre-concentrated extracts were obtained by solid phase extraction (SPE) using C18 cartridge. The results obviously showed that all pre-concentrated extracts performed on photovoltaic performances in DSSCs better than crude extracts except for mangosteen pericarp. The DSSC sensitized by pre-concentrated anthocyanin from roselle and red cabbage showed maximum current efficiency η = 0.71% while DSSC sensitized by crude anthocyanin from mangosteen pericarp reached maximum efficiency η = 0.97%. In addition, pre-concentrated extract based cells possess more stability than those of crude extract based cells. This indicates that pre-concentration of anthocyanin via SPE method is very effective for DSSCs based on good photovoltaic performance and stability. The DFT/TDDFT calculations of electronic and photoelectrochemical properties of the major anthocyanins found in the samples are employed to support the experimental results.

  3. Spin-adapted open-shell time-dependent density functional theory. II. Theory and pilot application.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian; Zhang, Yong; Suo, Bingbing

    2011-04-07

    The excited states of open-shell systems calculated by unrestricted Kohn-Sham-based time-dependent density functional theory (U-TD-DFT) are often heavily spin-contaminated and hence meaningless. This is solved ultimately by the recently proposed spin-adapted time-dependent density functional theory (TD-DFT) (S-TD-DFT) [J. Chem. Phys. 133, 064106 (2010)]. Unlike the standard restricted open-shell Kohn-Sham-based TD-DFT (R-TD-DFT) which can only access the singlet-coupled single excitations, the S-TD-DFT can capture both the singlet- and triplet-coupled single excitations with the same computational effort as the U-TD-DFT. The performances of the three approaches (U-TD-DFT, R-TD-DFT, and S-TD-DFT) are compared for both the spin-conserving and spin-flip excitations of prototypical open-shell systems, the nitrogen (N(2)(+)) and naphthalene (C(10)H(8)(+)) cations. The results show that the S-TD-DFT gives rise to balanced descriptions of excited states of open-shell systems.

  4. Computational design and experimental validation of new thermal barrier systems

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Shengmin [Louisiana State Univ., Baton Rouge, LA (United States)

    2015-03-31

    The focus of this project is on the development of a reliable and efficient ab initio based computational high temperature material design method which can be used to assist the Thermal Barrier Coating (TBC) bond-coat and top-coat design. Experimental evaluations on the new TBCs are conducted to confirm the new TBCs’ properties. Southern University is the subcontractor on this project with a focus on the computational simulation method development. We have performed ab initio density functional theory (DFT) method and molecular dynamics simulation on screening the top coats and bond coats for gas turbine thermal barrier coating design and validation applications. For experimental validations, our focus is on the hot corrosion performance of different TBC systems. For example, for one of the top coatings studied, we examined the thermal stability of TaZr2.75O8 and confirmed it’s hot corrosion performance.

  5. 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.

  6. Development of tight-binding based GW algorithm and its computational implementation for graphene

    Energy Technology Data Exchange (ETDEWEB)

    Majidi, Muhammad Aziz [Departemen Fisika, FMIPA, Universitas Indonesia, Kampus UI Depok (Indonesia); NUSNNI-NanoCore, Department of Physics, National University of Singapore (NUS), Singapore 117576 (Singapore); Singapore Synchrotron Light Source (SSLS), National University of Singapore (NUS), 5 Research Link, Singapore 117603 (Singapore); Naradipa, Muhammad Avicenna, E-mail: muhammad.avicenna11@ui.ac.id; Phan, Wileam Yonatan; Syahroni, Ahmad [Departemen Fisika, FMIPA, Universitas Indonesia, Kampus UI Depok (Indonesia); Rusydi, Andrivo [NUSNNI-NanoCore, Department of Physics, National University of Singapore (NUS), Singapore 117576 (Singapore); Singapore Synchrotron Light Source (SSLS), National University of Singapore (NUS), 5 Research Link, Singapore 117603 (Singapore)

    2016-04-19

    Graphene has been a hot subject of research in the last decade as it holds a promise for various applications. One interesting issue is whether or not graphene should be classified into a strongly or weakly correlated system, as the optical properties may change upon several factors, such as the substrate, voltage bias, adatoms, etc. As the Coulomb repulsive interactions among electrons can generate the correlation effects that may modify the single-particle spectra (density of states) and the two-particle spectra (optical conductivity) of graphene, we aim to explore such interactions in this study. The understanding of such correlation effects is important because eventually they play an important role in inducing the effective attractive interactions between electrons and holes that bind them into excitons. We do this study theoretically by developing a GW method implemented on the basis of the tight-binding (TB) model Hamiltonian. Unlike the well-known GW method developed within density functional theory (DFT) framework, our TB-based GW implementation may serve as an alternative technique suitable for systems which Hamiltonian is to be constructed through a tight-binding based or similar models. This study includes theoretical formulation of the Green’s function G, the renormalized interaction function W from random phase approximation (RPA), and the corresponding self energy derived from Feynman diagrams, as well as the development of the algorithm to compute those quantities. As an evaluation of the method, we perform calculations of the density of states and the optical conductivity of graphene, and analyze the results.

  7. Development of tight-binding based GW algorithm and its computational implementation for graphene

    International Nuclear Information System (INIS)

    Majidi, Muhammad Aziz; Naradipa, Muhammad Avicenna; Phan, Wileam Yonatan; Syahroni, Ahmad; Rusydi, Andrivo

    2016-01-01

    Graphene has been a hot subject of research in the last decade as it holds a promise for various applications. One interesting issue is whether or not graphene should be classified into a strongly or weakly correlated system, as the optical properties may change upon several factors, such as the substrate, voltage bias, adatoms, etc. As the Coulomb repulsive interactions among electrons can generate the correlation effects that may modify the single-particle spectra (density of states) and the two-particle spectra (optical conductivity) of graphene, we aim to explore such interactions in this study. The understanding of such correlation effects is important because eventually they play an important role in inducing the effective attractive interactions between electrons and holes that bind them into excitons. We do this study theoretically by developing a GW method implemented on the basis of the tight-binding (TB) model Hamiltonian. Unlike the well-known GW method developed within density functional theory (DFT) framework, our TB-based GW implementation may serve as an alternative technique suitable for systems which Hamiltonian is to be constructed through a tight-binding based or similar models. This study includes theoretical formulation of the Green’s function G, the renormalized interaction function W from random phase approximation (RPA), and the corresponding self energy derived from Feynman diagrams, as well as the development of the algorithm to compute those quantities. As an evaluation of the method, we perform calculations of the density of states and the optical conductivity of graphene, and analyze the results.

  8. Property-Based Anonymous Attestation in Trusted Cloud Computing

    Directory of Open Access Journals (Sweden)

    Zhen-Hu Ning

    2014-01-01

    Full Text Available In the remote attestation on Trusted Computer (TC computing mode TCCP, the trusted computer TC has an excessive burden, and anonymity and platform configuration information security of computing nodes cannot be guaranteed. To overcome these defects, based on the research on and analysis of current schemes, we propose an anonymous proof protocol based on property certificate. The platform configuration information is converted by the matrix algorithm into the property certificate, and the remote attestation is implemented by trusted ring signature scheme based on Strong RSA Assumption. By the trusted ring signature scheme based on property certificate, we achieve the anonymity of computing nodes and prevent the leakage of platform configuration information. By simulation, we obtain the computational efficiency of the scheme. We also expand the protocol and obtain the anonymous attestation based on ECC. By scenario comparison, we obtain the trusted ring signature scheme based on RSA, which has advantages with the growth of the ring numbers.

  9. Computer Based Modelling and Simulation

    Indian Academy of Sciences (India)

    GENERAL I ARTICLE. Computer Based ... universities, and later did system analysis, ... sonal computers (PC) and low cost software packages and tools. They can serve as useful learning experience through student projects. Models are .... Let us consider a numerical example: to calculate the velocity of a trainer aircraft ...

  10. Self-guaranteed measurement-based quantum computation

    Science.gov (United States)

    Hayashi, Masahito; Hajdušek, Michal

    2018-05-01

    In order to guarantee the output of a quantum computation, we usually assume that the component devices are trusted. However, when the total computation process is large, it is not easy to guarantee the whole system when we have scaling effects, unexpected noise, or unaccounted for correlations between several subsystems. If we do not trust the measurement basis or the prepared entangled state, we do need to be worried about such uncertainties. To this end, we propose a self-guaranteed protocol for verification of quantum computation under the scheme of measurement-based quantum computation where no prior-trusted devices (measurement basis or entangled state) are needed. The approach we present enables the implementation of verifiable quantum computation using the measurement-based model in the context of a particular instance of delegated quantum computation where the server prepares the initial computational resource and sends it to the client, who drives the computation by single-qubit measurements. Applying self-testing procedures, we are able to verify the initial resource as well as the operation of the quantum devices and hence the computation itself. The overhead of our protocol scales with the size of the initial resource state to the power of 4 times the natural logarithm of the initial state's size.

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

    Science.gov (United States)

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

    2011-02-28

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

  12. An Overview of Computer-Based Natural Language Processing.

    Science.gov (United States)

    Gevarter, William B.

    Computer-based Natural Language Processing (NLP) is the key to enabling humans and their computer-based creations to interact with machines using natural languages (English, Japanese, German, etc.) rather than formal computer languages. NLP is a major research area in the fields of artificial intelligence and computational linguistics. Commercial…

  13. 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.

  14. A quantum search algorithm of two entangled registers to realize quantum discrete Fourier transform of signal processing

    International Nuclear Information System (INIS)

    Pang Chaoyang; Hu Benqiong

    2008-01-01

    The discrete Fourier transform (DFT) is the base of modern signal processing. 1-dimensional fast Fourier transform (ID FFT) and 2D FFT have time complexity O (N log N) and O (N 2 log N) respectively. Since 1965, there has been no more essential breakthrough for the design of fast DFT algorithm. DFT has two properties. One property is that DFT is energy conservation transform. The other property is that many DFT coefficients are close to zero. The basic idea of this paper is that the generalized Grover's iteration can perform the computation of DFT which acts on the entangled states to search the big DFT coefficients until these big coefficients contain nearly all energy. One-dimensional quantum DFT (ID QDFT) and two-dimensional quantum DFT (2D QDFT) are presented in this paper. The quantum algorithm for convolution estimation is also presented in this paper. Compared with FFT, ID and 2D QDFT have time complexity O(√N) and O (N) respectively. QDFT and quantum convolution demonstrate that quantum computation to process classical signal is possible. (general)

  15. Environment-dependent crystal-field tight-binding based on density-functional theory

    International Nuclear Information System (INIS)

    Urban, Alexander

    2012-01-01

    Electronic structure calculations based on Kohn-Sham density-functional theory (DFT) allow the accurate prediction of chemical bonding and materials properties. Due to the high computational demand DFT calculations are, however, restricted to structures containing at most several hundreds of atoms, i.e., to length scales of a few nanometers. Though, many processes of technological relevance, for example in the field of nanoelectronics, are governed by phenomena that occur on a slightly larger length scale of up to 100 nanometers, which corresponds to tens of thousands of atoms. The semiempirical Slater-Koster tight-binding (TB) method makes it feasible to calculate the electronic structure of such large systems. In contrast to first-principles-based DFT, which is universally applicable to almost all chemical species, the TB method is based on parametrized models that are usually specialized for a particular application or for one certain class of compounds. Usually the model parameters (Slater-Koster tables) are empirically adjusted to reproduce either experimental reference data (e.g., geometries, elastic constants) or data from first-principles methods such as DFT. The construction of a new TB model is therefore connected with a considerable effort that is often contrasted by a low transferability of the parametrization. In this thesis we develop a systematic methodology for the derivation of accurate and transferable TB models from DFT calculations. Our procedure exploits the formal relationship between the two methods, according to which the TB total energy can be understood as a direct approximation of the Kohn--Sham energy functional. The concept of our method is different to previous approaches such as the DFTB method, since it allows to extract TB parameters from converged DFT wave functions and Hamiltonians of arbitrary reference structures. In the following the different subjects of this thesis are briefly summarized. We introduce a new technique for the

  16. Computational modeling of biodegradable starch based polymer composites

    Science.gov (United States)

    Joshi, Sachin Sudhakar

    2007-12-01

    Purpose. The goal of this study is to improve the favorable molecular interactions between starch and PPC by addition of grafting monomers MA and ROM as compatibilizers, which would advance the mechanical properties of starch/PPC composites. Methodology. DFT and semi-empirical methods based calculations were performed on three systems: (a) starch/PPC, (b) starch/PPC-MA, and (c) starch-ROM/PPC. Theoretical computations involved the determination of optimal geometries, binding-energies and vibrational frequencies of the blended polymers. Findings. Calculations performed on five starch/PPC composites revealed hydrogen bond formation as the driving force behind stable composite formation, also confirmed by the negative relative energies of the composites indicating the existence of binding forces between the constituent co-polymers. The interaction between starch and PPC is also confirmed by the computed decrease in stretching CO and OH group frequencies participating in hydrogen bond formation, which agree qualitatively with the experimental values. A three-step mechanism of grafting MA on PPC was proposed to improve the compatibility of PPC with starch. Nine types of 'blends' produced by covalent bond formation between starch and MA-grafted PPC were found to be energetically stable, with blends involving MA grafted at the 'B' and 'C' positions of PPC indicating a binding-energy increase of 6.8 and 6.2 kcal/mol, respectively, as compared to the non-grafted starch/PPC composites. A similar increase in binding-energies was also observed for three types of 'composites' formed by hydrogen bond formation between starch and MA-grafted PPC. Next, grafting of ROM on starch and subsequent blend formation with PPC was studied. All four types of blends formed by the reaction of ROM-grafted starch with PPC were found to be more energetically stable as compared to the starch/PPC composite and starch/PPC-MA composites and blends. A blend of PPC and ROM grafted at the '

  17. Spectroscopic and TD-DFT studies on the dual mode fluorescent chemosensors based on pyrene thiosemicarbazones, and its application as molecular-scale logic devices

    Energy Technology Data Exchange (ETDEWEB)

    Basheer, Sabeel M. [Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015 (India); Willis, Anthony C. [Research School of Chemistry, The Australian National University, Canberra, ACT 2601 (Australia); Sreekanth, Anandaram, E-mail: sreekanth@nitt.edu [Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015 (India)

    2017-03-15

    Two newly synthesised pyrene based molecules are hereby reported as molecular switches. The absorption and emission response for receptors with and without F{sup −}, CN{sup −} and Cu{sup 2+} ions can mimic multiple logic gate such as AND, NOR, XNOR, OR, XOR, INHIBITION and TRANSFER gates. The fluorescence reversibility was checked with the alternative addition of fluoride and calcium ions, which can be explained by the “Read-Erase-Read-Write” logic loop. The calculated binding constant value show PyBTSC is better chemosensor than PyCTSC, and the binding affinity is in the order of Cu{sup 2+}Г‹Ж’F{sup -}Г‹Ж’CN{sup −.} The detailed mechanism was investigated using DFT and TD-DFT calculations. The fluorescence quenching behaviour of receptor-F complex can be explained by PET mechanism along with ESPT process. The proton attached to the nitrogen which is adjacent to pyrene moiety is first make the hydrogen bond with fluoride ion at the excited state, which has confirmed by natural bond orbital (NBO) and potential energy surface (PES) analysis. - Graphical abstract: The newly synthesised thiocarbazone derivates used as an effective and selective colourimetric and “turn on” fluorescence sensor for copper ion and ‘turn off’ for fluoride and cyanide anion. The presence and absence of ions were considered as input signals and the corresponding absorption and emission responses were consired as output. The proton transfer from the nitrogen adjacent to pyrene moiety, and which takes place at the excited state (ESPT).

  18. 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.

  19. A Compute Environment of ABC95 Array Computer Based on Multi-FPGA Chip

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    ABC95 array computer is a multi-function network's computer based on FPGA technology, The multi-function network supports processors conflict-free access data from memory and supports processors access data from processors based on enhanced MESH network.ABC95 instruction's system includes control instructions, scalar instructions, vectors instructions.Mostly net-work instructions are introduced.A programming environment of ABC95 array computer assemble language is designed.A programming environment of ABC95 array computer for VC++ is advanced.It includes load function of ABC95 array computer program and data, store function, run function and so on.Specially, The data type of ABC95 array computer conflict-free access is defined.The results show that these technologies can develop programmer of ABC95 array computer effectively.

  20. Machine learning assisted first-principles calculation of multicomponent solid solutions: estimation of interface energy in Ni-based superalloys

    Science.gov (United States)

    Chandran, Mahesh; Lee, S. C.; Shim, Jae-Hyeok

    2018-02-01

    A disordered configuration of atoms in a multicomponent solid solution presents a computational challenge for first-principles calculations using density functional theory (DFT). The challenge is in identifying the few probable (low energy) configurations from a large configurational space before DFT calculation can be performed. The search for these probable configurations is possible if the configurational energy E({\\boldsymbol{σ }}) can be calculated accurately and rapidly (with a negligibly small computational cost). In this paper, we demonstrate such a possibility by constructing a machine learning (ML) model for E({\\boldsymbol{σ }}) trained with DFT-calculated energies. The feature vector for the ML model is formed by concatenating histograms of pair and triplet (only equilateral triangle) correlation functions, {g}(2)(r) and {g}(3)(r,r,r), respectively. These functions are a quantitative ‘fingerprint’ of the spatial arrangement of atoms, familiar in the field of amorphous materials and liquids. The ML model is used to generate an accurate distribution P(E({\\boldsymbol{σ }})) by rapidly spanning a large number of configurations. The P(E) contains full configurational information of the solid solution and can be selectively sampled to choose a few configurations for targeted DFT calculations. This new framework is employed to estimate (100) interface energy ({σ }{{IE}}) between γ and γ \\prime at 700 °C in Alloy 617, a Ni-based superalloy, with composition reduced to five components. The estimated {σ }{{IE}} ≈ 25.95 mJ m-2 is in good agreement with the value inferred by the precipitation model fit to experimental data. The proposed new ML-based ab initio framework can be applied to calculate the parameters and properties of alloys with any number of components, thus widening the reach of first-principles calculation to realistic compositions of industrially relevant materials and alloys.

  1. 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....

  2. 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.

  3. Transforming bases to bytes: Molecular computing with DNA

    Indian Academy of Sciences (India)

    Despite the popular image of silicon-based computers for computation, an embryonic field of mole- cular computation is emerging, where molecules in solution perform computational ..... [4] Mao C, Sun W, Shen Z and Seeman N C 1999. A nanomechanical device based on the B-Z transition of DNA; Nature 397 144–146.

  4. A Web-based Distributed Voluntary Computing Platform for Large Scale Hydrological Computations

    Science.gov (United States)

    Demir, I.; Agliamzanov, R.

    2014-12-01

    Distributed volunteer computing can enable researchers and scientist to form large parallel computing environments to utilize the computing power of the millions of computers on the Internet, and use them towards running large scale environmental simulations and models to serve the common good of local communities and the world. Recent developments in web technologies and standards allow client-side scripting languages to run at speeds close to native application, and utilize the power of Graphics Processing Units (GPU). Using a client-side scripting language like JavaScript, we have developed an open distributed computing framework that makes it easy for researchers to write their own hydrologic models, and run them on volunteer computers. Users will easily enable their websites for visitors to volunteer sharing their computer resources to contribute running advanced hydrological models and simulations. Using a web-based system allows users to start volunteering their computational resources within seconds without installing any software. The framework distributes the model simulation to thousands of nodes in small spatial and computational sizes. A relational database system is utilized for managing data connections and queue management for the distributed computing nodes. In this paper, we present a web-based distributed volunteer computing platform to enable large scale hydrological simulations and model runs in an open and integrated environment.

  5. 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.

  6. FT-Raman, FT-IR spectra and total energy distribution of 3-pentyl-2,6-diphenylpiperidin-4-one: DFT method.

    Science.gov (United States)

    Subashchandrabose, S; Saleem, H; Erdogdu, Y; Rajarajan, G; Thanikachalam, V

    2011-11-01

    FT-Raman and FT-IR spectra were recorded for 3-pentyl-2,6-diphenylpiperidin-4-one (PDPO) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and the Raman scattering intensities were computed using DFT/6-31G(d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the total energy distribution (TED) of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated and compared with X-ray diffraction data. This comparison was good agreement. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π* transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of the carbon, nitrogen and oxygen were calculated using same level of calculation. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Computer-Based Learning in Chemistry Classes

    Science.gov (United States)

    Pietzner, Verena

    2014-01-01

    Currently not many people would doubt that computers play an essential role in both public and private life in many countries. However, somewhat surprisingly, evidence of computer use is difficult to find in German state schools although other countries have managed to implement computer-based teaching and learning in their schools. This paper…

  8. Electrocatalytic aerobic epoxidation of alkenes: Experimental and DFT investigation

    International Nuclear Information System (INIS)

    Magdesieva, Tatiana V.; Borisova, Nataliya E.; Dolganov, Alexander V.; Ustynyuk, Yuri A.

    2012-01-01

    A new method for electrocatalytic aerobic epoxidation of alkenes catalyzed by binuclear Cu(II) complexes with azomethine ligands based on 2,6-diformyl-4-tert-butylphenol is described. In acetonitrile–water (5%), at the potential of Cu II /Cu I redox couple (–0.8 V vs. Ag/AgCl/KCl) at room temperature the epoxide is obtained in an average yield of around 50%. Contrary to the majority of known epoxidations, no strong oxidants are involved and no free hydrogen peroxide is formed in the reaction, thus making it ecologically friendly. The DFT quantum-chemical modeling of the reaction mechanism revealed that a copper hydroperoxo-complex rather than hydrogen peroxide or a copper oxo-complex oxidizes alkene. The process is very selective since neither products of hydroxylation of benzene ring in styrene nor of allylic oxidation of cyclohexene were detected.

  9. Music Learning Based on Computer Software

    Directory of Open Access Journals (Sweden)

    Baihui Yan

    2017-12-01

    Full Text Available In order to better develop and improve students’ music learning, the authors proposed the method of music learning based on computer software. It is still a new field to use computer music software to assist teaching. Hereby, we conducted an in-depth analysis on the computer-enabled music learning and the music learning status in secondary schools, obtaining the specific analytical data. Survey data shows that students have many cognitive problems in the current music classroom, and yet teachers have not found a reasonable countermeasure to them. Against this background, the introduction of computer music software to music learning is a new trial that can not only cultivate the students’ initiatives of music learning, but also enhance their abilities to learn music. Therefore, it is concluded that the computer software based music learning is of great significance to improving the current music learning modes and means.

  10. Novel Schemes for Measurement-Based Quantum Computation

    International Nuclear Information System (INIS)

    Gross, D.; Eisert, J.

    2007-01-01

    We establish a framework which allows one to construct novel schemes for measurement-based quantum computation. The technique develops tools from many-body physics--based on finitely correlated or projected entangled pair states--to go beyond the cluster-state based one-way computer. We identify resource states radically different from the cluster state, in that they exhibit nonvanishing correlations, can be prepared using nonmaximally entangling gates, or have very different local entanglement properties. In the computational models, randomness is compensated in a different manner. It is shown that there exist resource states which are locally arbitrarily close to a pure state. We comment on the possibility of tailoring computational models to specific physical systems

  11. Novel schemes for measurement-based quantum computation.

    Science.gov (United States)

    Gross, D; Eisert, J

    2007-06-01

    We establish a framework which allows one to construct novel schemes for measurement-based quantum computation. The technique develops tools from many-body physics-based on finitely correlated or projected entangled pair states-to go beyond the cluster-state based one-way computer. We identify resource states radically different from the cluster state, in that they exhibit nonvanishing correlations, can be prepared using nonmaximally entangling gates, or have very different local entanglement properties. In the computational models, randomness is compensated in a different manner. It is shown that there exist resource states which are locally arbitrarily close to a pure state. We comment on the possibility of tailoring computational models to specific physical systems.

  12. Epitaxial phase diagrams of SrTiO3, CaTiO3, and SrHfO3: Computational investigation including the role of antiferrodistortive and A -site displacement modes

    Science.gov (United States)

    Angsten, Thomas; Asta, Mark

    2018-04-01

    Ground-state epitaxial phase diagrams are calculated by density functional theory (DFT) for SrTiO3, CaTiO3, and SrHfO3 perovskite-based compounds, accounting for the effects of antiferrodistortive and A -site displacement modes. Biaxial strain states corresponding to epitaxial growth of (001)-oriented films are considered, with misfit strains ranging between -4 % and 4%. Ground-state structures are determined using a computational procedure in which input structures for DFT optimizations are identified as local minima in expansions of the total energy with respect to strain and soft-mode degrees of freedom. Comparison to results of previous DFT studies demonstrates the effectiveness of the computational approach in predicting ground-state phases. The calculated results show that antiferrodistortive octahedral rotations and associated A -site displacement modes act to suppress polarization and reduce the epitaxial strain energy. A projection of calculated atomic displacements in the ground-state epitaxial structures onto soft-mode eigenvectors shows that three ferroelectric and six antiferrodistortive displacement modes are dominant at all misfit strains considered, with the relative contributions from each varying systematically with the strain. Additional A -site displacement modes contribute to the atomic displacements in CaTiO3 and SrHfO3, which serve to optimize the coordination of the undersized A -site cation.

  13. An atom counting and electrophilicity based QSTR approach

    Indian Academy of Sciences (India)

    WINTEC

    QSTR models with two parameters result when global electrophilicity is used as the second descriptor. In ... Atom counting; QSTR; electrophilicity; conceptual DFT; Tetrahymena pyriformis. ... theoretical background whereas the computational.

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

    Science.gov (United States)

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

    2011-07-07

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

  15. Modeling soft factors in computer-based wargames

    Science.gov (United States)

    Alexander, Steven M.; Ross, David O.; Vinarskai, Jonathan S.; Farr, Steven D.

    2002-07-01

    Computer-based wargames have seen much improvement in recent years due to rapid increases in computing power. Because these games have been developed for the entertainment industry, most of these advances have centered on the graphics, sound, and user interfaces integrated into these wargames with less attention paid to the game's fidelity. However, for a wargame to be useful to the military, it must closely approximate as many of the elements of war as possible. Among the elements that are typically not modeled or are poorly modeled in nearly all military computer-based wargames are systematic effects, command and control, intelligence, morale, training, and other human and political factors. These aspects of war, with the possible exception of systematic effects, are individually modeled quite well in many board-based commercial wargames. The work described in this paper focuses on incorporating these elements from the board-based games into a computer-based wargame. This paper will also address the modeling and simulation of the systemic paralysis of an adversary that is implied by the concept of Effects Based Operations (EBO). Combining the fidelity of current commercial board wargames with the speed, ease of use, and advanced visualization of the computer can significantly improve the effectiveness of military decision making and education. Once in place, the process of converting board wargames concepts to computer wargames will allow the infusion of soft factors into military training and planning.

  16. Scavenging performance and antioxidant activity of γ-alumina nanoparticles towards DPPH free radical: Spectroscopic and DFT-D studies.

    Science.gov (United States)

    Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza

    2018-05-03

    The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base free radicals. Copyright © 2018. Published by Elsevier B.V.

  17. A DFT study of the effects of Sc doping on electronic and optical properties of CdS nanoparticles

    Directory of Open Access Journals (Sweden)

    Ur Rehman Shafiq

    2015-12-01

    Full Text Available In the present work a systematic study was carried out to understand the influence of Sc doping on electronic and optical properties of CdS nanoparticles. The geometry optimization and symmetry computation for CdS and Sc doped CdS nanoparticles using Density Functional Theory (DFT on B3LYP level with the QZ4P for Cd and DZ2P for sulphur and Sc were performed by Amsterdam Density Functional (ADF. The results show that HOMO-LUMO gap as well as electronic and optical properties of CdS clusters vary with Sc doping. The HOMO-LUMO gap is affected by the dopant and its value decreases to 0.6 eV. Through considering the numerical integration scheme in the ADF package, we investigated different vibrational modes and our calculated Raman and IR spectra are consistent with the reported result. The calculated IR and Raman peaks of CdS and Sc doped CdS clusters were in the range of 100 to 289 cm−1, 60 cm−1 to 350 cm−1 and 99 cm−1 to 282 cm−1, 60 cm−1 to 350 cm−1, respectively, which was also confirmed by experiment as well as a blue shift occurrence. Subsequently, for deeper research of pure and doped CdS clusters, their absorption spectra were calculated using time-dependent DFT method.

  18. Semantic computing and language knowledge bases

    Science.gov (United States)

    Wang, Lei; Wang, Houfeng; Yu, Shiwen

    2017-09-01

    As the proposition of the next-generation Web - semantic Web, semantic computing has been drawing more and more attention within the circle and the industries. A lot of research has been conducted on the theory and methodology of the subject, and potential applications have also been investigated and proposed in many fields. The progress of semantic computing made so far cannot be detached from its supporting pivot - language resources, for instance, language knowledge bases. This paper proposes three perspectives of semantic computing from a macro view and describes the current status of affairs about the construction of language knowledge bases and the related research and applications that have been carried out on the basis of these resources via a case study in the Institute of Computational Linguistics at Peking University.

  19. FOREWORD: Computational methodologies for designing materials Computational methodologies for designing materials

    Science.gov (United States)

    Rahman, Talat S.

    2009-02-01

    It would be fair to say that in the past few decades, theory and computer modeling have played a major role in elucidating the microscopic factors that dictate the properties of functional novel materials. Together with advances in experimental techniques, theoretical methods are becoming increasingly capable of predicting properties of materials at different length scales, thereby bringing in sight the long-sought goal of designing material properties according to need. Advances in computer technology and their availability at a reasonable cost around the world have made tit all the more urgent to disseminate what is now known about these modern computational techniques. In this special issue on computational methodologies for materials by design we have tried to solicit articles from authors whose works collectively represent the microcosm of developments in the area. This turned out to be a difficult task for a variety of reasons, not the least of which is space limitation in this special issue. Nevertheless, we gathered twenty articles that represent some of the important directions in which theory and modeling are proceeding in the general effort to capture the ability to produce materials by design. The majority of papers presented here focus on technique developments that are expected to uncover further the fundamental processes responsible for material properties, and for their growth modes and morphological evolutions. As for material properties, some of the articles here address the challenges that continue to emerge from attempts at accurate descriptions of magnetic properties, of electronically excited states, and of sparse matter, all of which demand new looks at density functional theory (DFT). I should hasten to add that much of the success in accurate computational modeling of materials emanates from the remarkable predictive power of DFT, without which we would not be able to place the subject on firm theoretical grounds. As we know and will also

  20. Computer Assisted Instructional Design for Computer-Based Instruction. Final Report. Working Papers.

    Science.gov (United States)

    Russell, Daniel M.; Pirolli, Peter

    Recent advances in artificial intelligence and the cognitive sciences have made it possible to develop successful intelligent computer-aided instructional systems for technical and scientific training. In addition, computer-aided design (CAD) environments that support the rapid development of such computer-based instruction have also been recently…

  1. 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.

  2. Effective one-body potential of DFT plus correlated kinetic energy density for two-electron spherical model atoms

    International Nuclear Information System (INIS)

    March, N.H.; Ludena, Eduardo V.

    2004-01-01

    For three model problems concerning two-electron spin-compensated ground states with spherical density, the third-order linear homogeneous differential equation constructed for the determination of ρ(r) is used here in conjunction with the von Weizsacker functional to characterize the one-body potential of density functional theory (DFT). Correlated von Weizsacker-type terms are compared to the exact DFT functional

  3. An Applet-based Anonymous Distributed Computing System.

    Science.gov (United States)

    Finkel, David; Wills, Craig E.; Ciaraldi, Michael J.; Amorin, Kevin; Covati, Adam; Lee, Michael

    2001-01-01

    Defines anonymous distributed computing systems and focuses on the specifics of a Java, applet-based approach for large-scale, anonymous, distributed computing on the Internet. Explains the possibility of a large number of computers participating in a single computation and describes a test of the functionality of the system. (Author/LRW)

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

    Directory of Open Access Journals (Sweden)

    Fabrine S. de Souza

    2015-05-01

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

  5. Ammonia-based quantum computer

    International Nuclear Information System (INIS)

    Ferguson, Andrew J.; Cain, Paul A.; Williams, David A.; Briggs, G. Andrew D.

    2002-01-01

    We propose a scheme for quantum computation using two eigenstates of ammonia or similar molecules. Individual ammonia molecules are confined inside fullerenes and used as two-level qubit systems. Interaction between these ammonia qubits takes place via the electric dipole moments, and in particular we show how a controlled-NOT gate could be implemented. After computation the qubit is measured with a single-electron electrometer sensitive enough to differentiate between the dipole moments of different states. We also discuss a possible implementation based on a quantum cellular automaton

  6. Genetic algorithm based approach to investigate doped metal oxide materials: Application to lanthanide-doped ceria

    Science.gov (United States)

    Hooper, James; Ismail, Arif; Giorgi, Javier B.; Woo, Tom K.

    2010-06-01

    A genetic algorithm (GA)-inspired method to effectively map out low-energy configurations of doped metal oxide materials is presented. Specialized mating and mutation operations that do not alter the identity of the parent metal oxide have been incorporated to efficiently sample the metal dopant and oxygen vacancy sites. The search algorithms have been tested on lanthanide-doped ceria (L=Sm,Gd,Lu) with various dopant concentrations. Using both classical and first-principles density-functional-theory (DFT) potentials, we have shown the methodology reproduces the results of recent systematic searches of doped ceria at low concentrations (3.2% L2O3 ) and identifies low-energy structures of concentrated samarium-doped ceria (3.8% and 6.6% L2O3 ) which relate to the experimental and theoretical findings published thus far. We introduce a tandem classical/DFT GA algorithm in which an inexpensive classical potential is first used to generate a fit gene pool of structures to enhance the overall efficiency of the computationally demanding DFT-based GA search.

  7. Acidity enhancement of niobia by sulfation: An experimental and DFT study

    International Nuclear Information System (INIS)

    Rocha, Angela S.; Costa, Gustavo C.; Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B.

    2017-01-01

    Acidic solids are used as catalyst at several industrial processes and studies to improve their activities have been developed by different groups. One method well known is sulfating oxide to create new acid sites, but investigations about sulfated niobia are still scarce. This work studied the influence of sulfation on the niobia acidity by using a very simple reaction model, the esterification of acetic acid with ethanol, performed at 60 °C and 1 atm. Niobia and sulfated niobia samples were characterized by N 2 adsorption, X-ray diffraction, FTIR and titration with n-butylamine. To investigate the nature of sulfate groups formed on the surface of niobia, calculations based on the Density Functional Theory (DFT) have been performed for two models: pure niobia with hydroxylated surface and sulfated niobia where one OH − surface group was replaced by a HSO 4 − . The experimental results indicated that the sulfation treatment leads to an increase in the specific surface area, acidity and, consequently, in the activity of niobia, with small changes in the crystal structure of the solid. The presence of sulfate groups was evidenced by FTIR spectra and calculations have indicated HSO 4 − species bounded to the surface. Density Functional Perturbation Theory (DFPT) was also employed to obtain infrared intensities in the region of sulfate vibration bands. - Highlights: • Sulfation treatment has improved the acidity of niobium oxide. • A sulfate group on niobia (T-Nb 2 O 5 ) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

  8. 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.

  9. Computer-based feedback in formative assessment

    NARCIS (Netherlands)

    van der Kleij, Fabienne

    2013-01-01

    Formative assessment concerns any assessment that provides feedback that is intended to support learning and can be used by teachers and/or students. Computers could offer a solution to overcoming obstacles encountered in implementing formative assessment. For example, computer-based assessments

  10. 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

  11. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John

    2016-03-29

    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2-phenylpyridine) using phenyl azide as nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during initial C-H bond cleavage) considered in pathway I (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four membered cyclic transition state. The vital role of base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.

  12. Combined experimental powder X-ray diffraction and DFT data to obtain the lowest energy molecular conformation of friedelin

    International Nuclear Information System (INIS)

    Oliveira, Djalma Menezes de; Mussel, Wagner da Nova; Duarte, Lucienir Pains; Silva, Gracia Divina de Fatima; Duarte, Helio Anderson; Gomes, Elionai Cassiana de Lima; Guimaraes, Luciana; Vieira Filho, Sidney A.

    2012-01-01

    Friedelin molecular conformers were obtained by Density Functional Theory (DFT) and by ab initio structure determination from powder X-ray diffraction. Their conformers with the five rings in chair-chair-chair-boat-boat, and with all rings in chair, are energy degenerated in gas-phase according to DFT results. The powder diffraction data reveals that rings A, B and C of friedelin are in chair, and rings D and E in boat-boat, conformation. The high correlation values among powder diffraction data, DFT and reported single crystal data indicate that the use of conventional X-ray diffractometer can be applied in routine laboratory analysis in the absence of a single-crystal diffractometer. (author)

  13. Combined experimental powder X-ray diffraction and DFT data to obtain the lowest energy molecular conformation of friedelin

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Djalma Menezes de; Mussel, Wagner da Nova; Duarte, Lucienir Pains; Silva, Gracia Divina de Fatima; Duarte, Helio Anderson; Gomes, Elionai Cassiana de Lima [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica; Guimaraes, Luciana [Universidade Federal de Sao Joao Del-Rei (UFSJ), MG (Brazil). Dept. de Ciencias Naturais; Vieira Filho, Sidney A., E-mail: bibo@ef.ufop.br [Universidade Federal de Ouro Preto (UFOP), MG (Brazil). Dept. de Farmacia

    2012-07-01

    Friedelin molecular conformers were obtained by Density Functional Theory (DFT) and by ab initio structure determination from powder X-ray diffraction. Their conformers with the five rings in chair-chair-chair-boat-boat, and with all rings in chair, are energy degenerated in gas-phase according to DFT results. The powder diffraction data reveals that rings A, B and C of friedelin are in chair, and rings D and E in boat-boat, conformation. The high correlation values among powder diffraction data, DFT and reported single crystal data indicate that the use of conventional X-ray diffractometer can be applied in routine laboratory analysis in the absence of a single-crystal diffractometer. (author)

  14. 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.

  15. DFT and EXAFS, mutually enhancing tools for structure elucidation of Tc complexes

    International Nuclear Information System (INIS)

    Breynaert, E.; Bruggeman, C.; Maes, A.

    2005-01-01

    Full text of publication follows: The redox-sensitive fission product technetium-99 (Tc) is of great interest in nuclear waste disposal studies because of its potential for contaminating the geosphere due to its very long half-life (2.13 x 10 5 year) and high mobility under oxidising conditions, where technetium forms pertechnetate (TcO 4 - ). Under suitable reducing conditions, e.g. in the presence of an iron(II) containing solid phase which can act as an electron donor, the solubility can be limited by the reduction of pertechnetate followed by the formation of a surface precipitate [1]. However, by association with mobile humic substances (HS) or other associating/complexing species, the solubility of reduced Tc species may be drastically enhanced [2]. The elucidation of the identity and geometrical structure of the species causing this enhanced solubility often remains a difficult issue. Extended X-Ray Absorption Fluorescence Spectroscopy/ X-Ray Absorption Near Edge Spectroscopy (EXAFS/XANES) analysis can be very helpful to determine the molecular surroundings of reduced Tc organic complexes of Tc(IV) colloid-HS-associations. The interpretation of the EXAFS spectra is however not a straightforward process due to the possibly strong influence of multiple scattering paths on the spectra. Contrary to single scattering analysis which can be easily performed on the experimental EXAFS spectra, multiple scattering analysis can only be done, based on good approximations of the possible geometrical structures of the species under consideration. It has been shown that the Density Functional Theory (DFT) can be used to perform geometry optimizations of technetium species and therefore can be utilized to predict the structure of technetium complexes [3]. The success and computational effort needed for such structure predictions are however highly dependant on the quality of the initial structure from which the geometry optimization is started. Single scattering analysis of

  16. 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.

  17. Design Principles for the Atomic and Electronic Structure of Halide Perovskite Photovoltaic Materials: Insights from Computation.

    Science.gov (United States)

    Berger, Robert F

    2018-02-09

    In the current decade, perovskite solar cell research has emerged as a remarkably active, promising, and rapidly developing field. Alongside breakthroughs in synthesis and device engineering, halide perovskite photovoltaic materials have been the subject of predictive and explanatory computational work. In this Minireview, we focus on a subset of this computation: density functional theory (DFT)-based work highlighting the ways in which the electronic structure and band gap of this class of materials can be tuned via changes in atomic structure. We distill this body of computational literature into a set of underlying design principles for the band gap engineering of these materials, and rationalize these principles from the viewpoint of band-edge orbital character. We hope that this perspective provides guidance and insight toward the rational design and continued improvement of perovskite photovoltaics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Computational aeroelasticity using a pressure-based solver

    Science.gov (United States)

    Kamakoti, Ramji

    A computational methodology for performing fluid-structure interaction computations for three-dimensional elastic wing geometries is presented. The flow solver used is based on an unsteady Reynolds-Averaged Navier-Stokes (RANS) model. A well validated k-ε turbulence model with wall function treatment for near wall region was used to perform turbulent flow calculations. Relative merits of alternative flow solvers were investigated. The predictor-corrector-based Pressure Implicit Splitting of Operators (PISO) algorithm was found to be computationally economic for unsteady flow computations. Wing structure was modeled using Bernoulli-Euler beam theory. A fully implicit time-marching scheme (using the Newmark integration method) was used to integrate the equations of motion for structure. Bilinear interpolation and linear extrapolation techniques were used to transfer necessary information between fluid and structure solvers. Geometry deformation was accounted for by using a moving boundary module. The moving grid capability was based on a master/slave concept and transfinite interpolation techniques. Since computations were performed on a moving mesh system, the geometric conservation law must be preserved. This is achieved by appropriately evaluating the Jacobian values associated with each cell. Accurate computation of contravariant velocities for unsteady flows using the momentum interpolation method on collocated, curvilinear grids was also addressed. Flutter computations were performed for the AGARD 445.6 wing at subsonic, transonic and supersonic Mach numbers. Unsteady computations were performed at various dynamic pressures to predict the flutter boundary. Results showed favorable agreement of experiment and previous numerical results. The computational methodology exhibited capabilities to predict both qualitative and quantitative features of aeroelasticity.

  19. 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.

  20. Computer Based Expert Systems.

    Science.gov (United States)

    Parry, James D.; Ferrara, Joseph M.

    1985-01-01

    Claims knowledge-based expert computer systems can meet needs of rural schools for affordable expert advice and support and will play an important role in the future of rural education. Describes potential applications in prediction, interpretation, diagnosis, remediation, planning, monitoring, and instruction. (NEC)

  1. 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...

  2. 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

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

    Directory of Open Access Journals (Sweden)

    Andrea Alparone

    2013-01-01

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

  4. CSNS computing environment Based on OpenStack

    Science.gov (United States)

    Li, Yakang; Qi, Fazhi; Chen, Gang; Wang, Yanming; Hong, Jianshu

    2017-10-01

    Cloud computing can allow for more flexible configuration of IT resources and optimized hardware utilization, it also can provide computing service according to the real need. We are applying this computing mode to the China Spallation Neutron Source(CSNS) computing environment. So, firstly, CSNS experiment and its computing scenarios and requirements are introduced in this paper. Secondly, the design and practice of cloud computing platform based on OpenStack are mainly demonstrated from the aspects of cloud computing system framework, network, storage and so on. Thirdly, some improvments to openstack we made are discussed further. Finally, current status of CSNS cloud computing environment are summarized in the ending of this paper.

  5. 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.

  6. 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

  7. 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.

  8. Computationally simple, analytic, closed form solution of the Coulomb self-interaction problem in Kohn Sham density functional theory

    International Nuclear Information System (INIS)

    Gonis, Antonios; Daene, Markus W.; Nicholson, Don M.; Stocks, George Malcolm

    2012-01-01

    We have developed and tested in terms of atomic calculations an exact, analytic and computationally simple procedure for determining the functional derivative of the exchange energy with respect to the density in the implementation of the Kohn Sham formulation of density functional theory (KS-DFT), providing an analytic, closed-form solution of the self-interaction problem in KS-DFT. We demonstrate the efficacy of our method through ground-state calculations of the exchange potential and energy for atomic He and Be atoms, and comparisons with experiment and the results obtained within the optimized effective potential (OEP) method.

  9. A Computational Experiment of the Endo versus Exo Preference in a Diels-Alder Reaction

    Science.gov (United States)

    Rowley, Christopher N.; Woo, Tom K.

    2009-01-01

    We have developed and tested a computational laboratory that investigates an endo versus exo Diels-Alder cycloaddition. This laboratory employed density functional theory (DFT) calculations to study the cycloaddition of N-phenylmaleimide to furan. The endo and exo stereoisomers of the product were distinguished by building the two isomers in a…

  10. 1-(2-Chlorobenzyloxy-3-[1,2,3]triazol-1-yl-propan-2-ol Derivatives: Synthesis, Characterization, and DFT-Based Descriptors Analysis

    Directory of Open Access Journals (Sweden)

    Eloisa Román-Maldonado

    2017-01-01

    Full Text Available A novel series of 1-(2-chlorobenzyloxy-3-[1,2,3]triazol-1-yl-propan-2-ol derivatives was designed and synthesized using copper catalyzed alkyne-azide cycloaddition in the key step. Theoretical investigation of molecular and electronic properties by means of global and local reactivity indexes of the synthetized compounds was carried out, using DFT (Density Functional Theory at PBEPBE/6-31++G⁎⁎ level.

  11. A Reinvestigation of the Ionic Liquid Diisopropylethylammonium Formate by NMR and DFT Methods

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Lund, Torben; Krake, Jacob

    2016-01-01

    The complex between diisopropylethylamine (DIPEA) and formic acid has been reinvestigated. Mixing the compounds in the ratio 1:1 leads to a phase separation in which the upper phase is DIPEA, the lower phase is the “ionic liquid” named DIPEF. A combined NMR and DFT study shows that the lower phase...... that presented elsewhere. However, the present picture should be considered using acids and bases with a pKa difference less than 8. The formic acid content in the DIPEF ionic liquid causes desorption of the dye-sensitized solar cell (DSC) dye N719 from the photo anode and DIPEF is therefore not a suitable...

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

    Science.gov (United States)

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

    2017-11-01

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

  13. 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.

  14. A novel proof of the DFT formula for the interatomic force field of Molecular Dynamics

    International Nuclear Information System (INIS)

    Morante, S.; Rossi, G.C.

    2017-01-01

    We give a novel and simple proof of the DFT expression for the interatomic force field that drives the motion of atoms in classical Molecular Dynamics, based on the observation that the ground state electronic energy, seen as a functional of the external potential, is the Legendre transform of the Hohenberg–Kohn functional, which in turn is a functional of the electronic density. We show in this way that the so-called Hellmann–Feynman analytical formula, currently used in numerical simulations, actually provides the exact expression of the interatomic force.

  15. A novel proof of the DFT formula for the interatomic force field of Molecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Morante, S., E-mail: morante@roma2.infn.it [Dipartimento di Fisica, Università di Roma, “ Tor Vergata ”, INFN, Sezione di Roma 2, Via della Ricerca Scientifica - 00133 Roma (Italy); Rossi, G.C., E-mail: rossig@roma2.infn.it [Dipartimento di Fisica, Università di Roma, “ Tor Vergata ”, INFN, Sezione di Roma 2, Via della Ricerca Scientifica - 00133 Roma (Italy); Centro Fermi-Museo Storico della Fisica e Centro Studi e Ricerche E. Fermi, Compendio del Viminale, Piazza del Viminale 1, I-00184 Rome (Italy)

    2017-02-15

    We give a novel and simple proof of the DFT expression for the interatomic force field that drives the motion of atoms in classical Molecular Dynamics, based on the observation that the ground state electronic energy, seen as a functional of the external potential, is the Legendre transform of the Hohenberg–Kohn functional, which in turn is a functional of the electronic density. We show in this way that the so-called Hellmann–Feynman analytical formula, currently used in numerical simulations, actually provides the exact expression of the interatomic force.

  16. Computer-Based Career Interventions.

    Science.gov (United States)

    Mau, Wei-Cheng

    The possible utilities and limitations of computer-assisted career guidance systems (CACG) have been widely discussed although the effectiveness of CACG has not been systematically considered. This paper investigates the effectiveness of a theory-based CACG program, integrating Sequential Elimination and Expected Utility strategies. Three types of…

  17. Music Learning Based on Computer Software

    OpenAIRE

    Baihui Yan; Qiao Zhou

    2017-01-01

    In order to better develop and improve students’ music learning, the authors proposed the method of music learning based on computer software. It is still a new field to use computer music software to assist teaching. Hereby, we conducted an in-depth analysis on the computer-enabled music learning and the music learning status in secondary schools, obtaining the specific analytical data. Survey data shows that students have many cognitive problems in the current music classroom, and yet teach...

  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. 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.

  20. Computer-based literature search in medical institutions in India

    Directory of Open Access Journals (Sweden)

    Kalita Jayantee

    2007-01-01

    Full Text Available Aim: To study the use of computer-based literature search and its application in clinical training and patient care as a surrogate marker of evidence-based medicine. Materials and Methods: A questionnaire comprising of questions on purpose (presentation, patient management, research, realm (site accessed, nature and frequency of search, effect, infrastructure, formal training in computer based literature search and suggestions for further improvement were sent to residents and faculty of a Postgraduate Medical Institute (PGI and a Medical College. The responses were compared amongst different subgroups of respondents. Results: Out of 300 subjects approached 194 responded; of whom 103 were from PGI and 91 from Medical College. There were 97 specialty residents, 58 super-specialty residents and 39 faculty members. Computer-based literature search was done at least once a month by 89% though there was marked variability in frequency and extent. The motivation for computer-based literature search was for presentation in 90%, research in 65% and patient management in 60.3%. The benefit of search was acknowledged in learning and teaching by 80%, research by 65% and patient care by 64.4% of respondents. Formal training in computer based literature search was received by 41% of whom 80% were residents. Residents from PGI did more frequent and more extensive computer-based literature search, which was attributed to better infrastructure and training. Conclusion: Training and infrastructure both are crucial for computer-based literature search, which may translate into evidence based medicine.

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

    Science.gov (United States)

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

    2018-03-05

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

  2. 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.

  3. Acidity enhancement of niobia by sulfation: An experimental and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rocha, Angela S., E-mail: angela.sanches.rocha@gmail.com [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Costa, Gustavo C. [Universidade do Estado do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil); Tamiasso-Martinhon, Priscila; Sousa, Célia; Rocha, Alexandre B. [Universidade Federal do Rio de Janeiro, Departamento de Físico-Química, Instituto de Química, Rio de Janeiro (Brazil)

    2017-01-15

    Acidic solids are used as catalyst at several industrial processes and studies to improve their activities have been developed by different groups. One method well known is sulfating oxide to create new acid sites, but investigations about sulfated niobia are still scarce. This work studied the influence of sulfation on the niobia acidity by using a very simple reaction model, the esterification of acetic acid with ethanol, performed at 60 °C and 1 atm. Niobia and sulfated niobia samples were characterized by N{sub 2} adsorption, X-ray diffraction, FTIR and titration with n-butylamine. To investigate the nature of sulfate groups formed on the surface of niobia, calculations based on the Density Functional Theory (DFT) have been performed for two models: pure niobia with hydroxylated surface and sulfated niobia where one OH{sup −} surface group was replaced by a HSO{sub 4}{sup −}. The experimental results indicated that the sulfation treatment leads to an increase in the specific surface area, acidity and, consequently, in the activity of niobia, with small changes in the crystal structure of the solid. The presence of sulfate groups was evidenced by FTIR spectra and calculations have indicated HSO{sub 4}{sup −} species bounded to the surface. Density Functional Perturbation Theory (DFPT) was also employed to obtain infrared intensities in the region of sulfate vibration bands. - Highlights: • Sulfation treatment has improved the acidity of niobium oxide. • A sulfate group on niobia (T-Nb{sub 2}O{sub 5}) was proposed using DFT method. • Niobia and sulfated niobia are used for esterification of acetic acid with ethanol.

  4. Computer-based control systems of nuclear power plants

    International Nuclear Information System (INIS)

    Kalashnikov, V.K.; Shugam, R.A.; Ol'shevsky, Yu.N.

    1975-01-01

    Computer-based control systems of nuclear power plants may be classified into those using computers for data acquisition only, those using computers for data acquisition and data processing, and those using computers for process control. In the present paper a brief review is given of the functions the systems above mentioned perform, their applications in different nuclear power plants, and some of their characteristics. The trend towards hierarchic systems using control computers with reserves already becomes clear when consideration is made of the control systems applied in the Canadian nuclear power plants that pertain to the first ones equipped with process computers. The control system being now under development for the large Soviet reactors of WWER type will also be based on the use of control computers. That part of the system concerned with controlling the reactor assembly is described in detail

  5. A new Density Functional Theory (DFT) based method for supporting the assignment of vibrational signatures of mannan and cellulose—Analysis of palm kernel cake hydrolysis by ATR-FT-IR spectroscopy as a case study

    DEFF Research Database (Denmark)

    Barsberg, Søren Talbro; Sanadi, Anand Ramesh; Jørgensen, Henning

    2011-01-01

    Attenuated Total Reflectance (ATR) FT-IR spectroscopy gives in situ information on molecular concentration, organization and interactions in plant cell walls. We demonstrate its potential for further developments by a case study which combines ATR-FT-IR spectroscopy with a recently published DFT...... a decreasing degree of polymerization to be a plausible cause, although others may interfere. Keywords: Cellulose; Mannan; FT-IR; DFT; Molecular modelling; Palm kernel...

  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. Basicities of Strong Bases in Water: A Computational Study

    OpenAIRE

    Kaupmees, Karl; Trummal, Aleksander; Leito, Ivo

    2014-01-01

    Aqueous pKa values of strong organic bases – DBU, TBD, MTBD, different phosphazene bases, etc – were computed with CPCM, SMD and COSMO-RS approaches. Explicit solvent molecules were not used. Direct computations and computations with reference pKa values were used. The latter were of two types: (1) reliable experimental aqueous pKa value of a reference base with structure similar to the investigated base or (2) reliable experimental pKa value in acetonitrile of the investigated base itself. ...

  8. Anharmonic Infrared Spectroscopy through the Fourier Transform of Time Correlation Function Formalism in ONETEP.

    Science.gov (United States)

    Vitale, Valerio; Dziedzic, Jacek; Dubois, Simon M-M; Fangohr, Hans; Skylaris, Chris-Kriton

    2015-07-14

    Density functional theory molecular dynamics (DFT-MD) provides an efficient framework for accurately computing several types of spectra. The major benefit of DFT-MD approaches lies in the ability to naturally take into account the effects of temperature and anharmonicity, without having to introduce any ad hoc or a posteriori corrections. Consequently, computational spectroscopy based on DFT-MD approaches plays a pivotal role in the understanding and assignment of experimental peaks and bands at finite temperature, particularly in the case of floppy molecules. Linear-scaling DFT methods can be used to study large and complex systems, such as peptides, DNA strands, amorphous solids, and molecules in solution. Here, we present the implementation of DFT-MD IR spectroscopy in the ONETEP linear-scaling code. In addition, two methods for partitioning the dipole moment within the ONETEP framework are presented. Dipole moment partitioning allows us to compute spectra of molecules in solution, which fully include the effects of the solvent, while at the same time removing the solvent contribution from the spectra.

  9. Vector Radix 2 × 2 Sliding Fast Fourier Transform

    Directory of Open Access Journals (Sweden)

    Keun-Yung Byun

    2016-01-01

    Full Text Available The two-dimensional (2D discrete Fourier transform (DFT in the sliding window scenario has been successfully used for numerous applications requiring consecutive spectrum analysis of input signals. However, the results of conventional sliding DFT algorithms are potentially unstable because of the accumulated numerical errors caused by recursive strategy. In this letter, a stable 2D sliding fast Fourier transform (FFT algorithm based on the vector radix (VR 2 × 2 FFT is presented. In the VR-2 × 2 FFT algorithm, each 2D DFT bin is hierarchically decomposed into four sub-DFT bins until the size of the sub-DFT bins is reduced to 2 × 2; the output DFT bins are calculated using the linear combination of the sub-DFT bins. Because the sub-DFT bins for the overlapped input signals between the previous and current window are the same, the proposed algorithm reduces the computational complexity of the VR-2 × 2 FFT algorithm by reusing previously calculated sub-DFT bins in the sliding window scenario. Moreover, because the resultant DFT bins are identical to those of the VR-2 × 2 FFT algorithm, numerical errors do not arise; therefore, unconditional stability is guaranteed. Theoretical analysis shows that the proposed algorithm has the lowest computational requirements among the existing stable sliding DFT algorithms.

  10. Complexes of DNA bases and Watson-Crick base pairs interaction with neutral silver Agn (n = 8, 10, 12) clusters: a DFT and TDDFT study.

    Science.gov (United States)

    Srivastava, Ruby

    2018-03-01

    We study the binding of the neutral Ag n (n = 8, 10, 12) to the DNA base-adenine (A), guanine (G) and Watson-Crick -adenine-thymine, guanine-cytosine pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential was used for silver and 6-31 + G ** was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Ag n -A,G/WC complexes were also studied using time-dependent density functional theory. The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Ag n -WC complexes. The vertical ionization potential, vertical electron affinity, hardness, and electrophilicity index of Ag n -DNA/WC complexes have also been discussed.

  11. Method and system for dynamic probabilistic risk assessment

    Science.gov (United States)

    Dugan, Joanne Bechta (Inventor); Xu, Hong (Inventor)

    2013-01-01

    The DEFT methodology, system and computer readable medium extends the applicability of the PRA (Probabilistic Risk Assessment) methodology to computer-based systems, by allowing DFT (Dynamic Fault Tree) nodes as pivot nodes in the Event Tree (ET) model. DEFT includes a mathematical model and solution algorithm, supports all common PRA analysis functions and cutsets. Additional capabilities enabled by the DFT include modularization, phased mission analysis, sequence dependencies, and imperfect coverage.

  12. 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...

  13. Secure Data Access Control for Fog Computing Based on Multi-Authority Attribute-Based Signcryption with Computation Outsourcing and Attribute Revocation.

    Science.gov (United States)

    Xu, Qian; Tan, Chengxiang; Fan, Zhijie; Zhu, Wenye; Xiao, Ya; Cheng, Fujia

    2018-05-17

    Nowadays, fog computing provides computation, storage, and application services to end users in the Internet of Things. One of the major concerns in fog computing systems is how fine-grained access control can be imposed. As a logical combination of attribute-based encryption and attribute-based signature, Attribute-based Signcryption (ABSC) can provide confidentiality and anonymous authentication for sensitive data and is more efficient than traditional "encrypt-then-sign" or "sign-then-encrypt" strategy. Thus, ABSC is suitable for fine-grained access control in a semi-trusted cloud environment and is gaining more and more attention recently. However, in many existing ABSC systems, the computation cost required for the end users in signcryption and designcryption is linear with the complexity of signing and encryption access policy. Moreover, only a single authority that is responsible for attribute management and key generation exists in the previous proposed ABSC schemes, whereas in reality, mostly, different authorities monitor different attributes of the user. In this paper, we propose OMDAC-ABSC, a novel data access control scheme based on Ciphertext-Policy ABSC, to provide data confidentiality, fine-grained control, and anonymous authentication in a multi-authority fog computing system. The signcryption and designcryption overhead for the user is significantly reduced by outsourcing the undesirable computation operations to fog nodes. The proposed scheme is proven to be secure in the standard model and can provide attribute revocation and public verifiability. The security analysis, asymptotic complexity comparison, and implementation results indicate that our construction can balance the security goals with practical efficiency in computation.

  14. Computer-based learning for the enhancement of breastfeeding ...

    African Journals Online (AJOL)

    In this study, computer-based learning (CBL) was explored in the context of breastfeeding training for undergraduate Dietetic students. Aim: To adapt and validate an Indian computer-based undergraduate breastfeeding training module for use by South African undergraduate Dietetic students. Methods and materials: The ...

  15. Accelerating atomic orbital-based electronic structure calculation via pole expansion and selected inversion

    International Nuclear Information System (INIS)

    Lin, Lin; Yang, Chao; Chen, Mohan; He, Lixin

    2013-01-01

    We describe how to apply the recently developed pole expansion and selected inversion (PEXSI) technique to Kohn–Sham density function theory (DFT) electronic structure calculations that are based on atomic orbital discretization. We give analytic expressions for evaluating the charge density, the total energy, the Helmholtz free energy and the atomic forces (including both the Hellmann–Feynman force and the Pulay force) without using the eigenvalues and eigenvectors of the Kohn–Sham Hamiltonian. We also show how to update the chemical potential without using Kohn–Sham eigenvalues. The advantage of using PEXSI is that it has a computational complexity much lower than that associated with the matrix diagonalization procedure. We demonstrate the performance gain by comparing the timing of PEXSI with that of diagonalization on insulating and metallic nanotubes. For these quasi-1D systems, the complexity of PEXSI is linear with respect to the number of atoms. This linear scaling can be observed in our computational experiments when the number of atoms in a nanotube is larger than a few hundreds. Both the wall clock time and the memory requirement of PEXSI are modest. This even makes it possible to perform Kohn–Sham DFT calculations for 10 000-atom nanotubes with a sequential implementation of the selected inversion algorithm. We also perform an accurate geometry optimization calculation on a truncated (8, 0) boron nitride nanotube system containing 1024 atoms. Numerical results indicate that the use of PEXSI does not lead to loss of the accuracy required in a practical DFT calculation. (paper)

  16. Fischer-Tropsch Synthesis on Multicomponent Catalysts: What Can We Learn from Computer Simulations?

    Directory of Open Access Journals (Sweden)

    José L. C. Fajín

    2015-01-01

    Full Text Available In this concise review paper, we will address recent studies based on the generalized-gradient approximation (GGA of the density functional theory (DFT and on the periodic slab approach devoted to the understanding of the Fischer-Tropsch synthesis process on transition metal catalysts. As it will be seen, this computational combination arises as a very adequate strategy for the study of the reaction mechanisms on transition metal surfaces under well-controlled conditions and allows separating the influence of different parameters, e.g., catalyst surface morphology and coverage, influence of co-adsorbates, among others, in the global catalytic processes. In fact, the computational studies can now compete with research employing modern experimental techniques since very efficient parallel computer codes and powerful computers enable the investigation of more realistic molecular systems in terms of size and composition and to explore the complexity of the potential energy surfaces connecting reactants, to intermediates, to products of reaction. In the case of the Fischer-Tropsch process, the calculations were used to complement experimental work and to clarify the reaction mechanisms on different catalyst models, as well as the influence of additional components and co-adsorbate species in catalyst activity and selectivity.

  17. 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.

  18. Silicon CMOS architecture for a spin-based quantum computer.

    Science.gov (United States)

    Veldhorst, M; Eenink, H G J; Yang, C H; Dzurak, A S

    2017-12-15

    Recent advances in quantum error correction codes for fault-tolerant quantum computing and physical realizations of high-fidelity qubits in multiple platforms give promise for the construction of a quantum computer based on millions of interacting qubits. However, the classical-quantum interface remains a nascent field of exploration. Here, we propose an architecture for a silicon-based quantum computer processor based on complementary metal-oxide-semiconductor (CMOS) technology. We show how a transistor-based control circuit together with charge-storage electrodes can be used to operate a dense and scalable two-dimensional qubit system. The qubits are defined by the spin state of a single electron confined in quantum dots, coupled via exchange interactions, controlled using a microwave cavity, and measured via gate-based dispersive readout. We implement a spin qubit surface code, showing the prospects for universal quantum computation. We discuss the challenges and focus areas that need to be addressed, providing a path for large-scale quantum computing.

  19. Complexation of the lithium cation with beauvericin: experimental and DFT study

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Toman, Petr; Vaňura, P.

    2012-01-01

    Roč. 1024, 26 September (2012), s. 142-145 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GAP205/10/2280 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : extraction * DFT * complexation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.404, year: 2012

  20. N,N′-Dipyridoxyl(1,8-diamino-3,6-dioxaoctane Schiff-base: Synthesis, experimental and theoretical identification

    Directory of Open Access Journals (Sweden)

    M.J. Khoshkholgh

    2013-05-01

    Full Text Available The N,N′-dipyridoxyl(1,8-diamino-3,6-dioxaoctane (=H2L Schiff-base has been synthesized and characterized by IR, 1H NMR, mass spectrometry and elemental analysis. Its optimized geometry and theoretical vibrational frequencies have been computed using density functional theory (DFT method via the B3LYP functional. Also, its 1H and 13C NMR chemical shifts have been calculated at the same computational level. In optimized geometry of the H2L, the two pyridine rings are perpendicular to each other. The phenolic hydrogens are engaged in intramolecular-hydrogen bonds with the azomethine nitrogens.

  1. 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

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

    Science.gov (United States)

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

    2016-02-24

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  4. A polarizable QM/MM approach to the molecular dynamics of amide groups solvated in water

    Energy Technology Data Exchange (ETDEWEB)

    Schwörer, Magnus; Wichmann, Christoph; Tavan, Paul, E-mail: tavan@physik.uni-muenchen.de [Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians Universität München, Oettingenstr. 67, 80538 München (Germany)

    2016-03-21

    The infrared (IR) spectra of polypeptides are dominated by the so-called amide bands. Because they originate from the strongly polar and polarizable amide groups (AGs) making up the backbone, their spectral positions sensitively depend on the local electric fields. Aiming at accurate computations of these IR spectra by molecular dynamics (MD) simulations, which derive atomic forces from a hybrid quantum and molecular mechanics (QM/MM) Hamiltonian, here we consider the effects of solvation in bulk liquid water on the amide bands of the AG model compound N-methyl-acetamide (NMA). As QM approach to NMA we choose grid-based density functional theory (DFT). For the surrounding MM water, we develop, largely based on computations, a polarizable molecular mechanics (PMM) model potential called GP6P, which features six Gaussian electrostatic sources (one induced dipole, five static partial charge distributions) and, therefore, avoids spurious distortions of the DFT electron density in hybrid DFT/PMM simulations. Bulk liquid GP6P is shown to have favorable properties at the thermodynamic conditions of the parameterization and beyond. Lennard-Jones (LJ) parameters of the DFT fragment NMA are optimized by comparing radial distribution functions in the surrounding GP6P liquid with reference data obtained from a “first-principles” DFT-MD simulation. Finally, IR spectra of NMA in GP6P water are calculated from extended DFT/PMM-MD trajectories, in which the NMA is treated by three different DFT functionals (BP, BLYP, B3LYP). Method-specific frequency scaling factors are derived from DFT-MD simulations of isolated NMA. The DFT/PMM-MD simulations with GP6P and with the optimized LJ parameters then excellently predict the effects of aqueous solvation and deuteration observed in the IR spectra of NMA. As a result, the methods required to accurately compute such spectra by DFT/PMM-MD also for larger peptides in aqueous solution are now at hand.

  5. Transitions in the computational power of thermal states for measurement-based quantum computation

    International Nuclear Information System (INIS)

    Barrett, Sean D.; Bartlett, Stephen D.; Jennings, David; Doherty, Andrew C.; Rudolph, Terry

    2009-01-01

    We show that the usefulness of the thermal state of a specific spin-lattice model for measurement-based quantum computing exhibits a transition between two distinct 'phases' - one in which every state is a universal resource for quantum computation, and another in which any local measurement sequence can be simulated efficiently on a classical computer. Remarkably, this transition in computational power does not coincide with any phase transition, classical, or quantum in the underlying spin-lattice model.

  6. 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...

  7. A DFT study of cyclopropane adsorption on Pt(1 1 1). Electronic structure and bonding

    International Nuclear Information System (INIS)

    Germán, E.; López-Corral, I.; Pirillo, S.; Juan, A.; Brizuela, G.

    2014-01-01

    We have studied the adsorption of cyclopropane (c-C 3 H 6 ) on Pt(1 1 1) by means of the density functional theory (DFT). We have investigated the preferential adsorption geometry, considering different adsorption sites and bonding configurations for the molecular adsorbate. We have also computed the electronic structure and bonding interactions by means of density of states (DOS), crystal orbital overlap population (OPDOS), and overlap population (OP) analysis. Our results show a small preference for Bridge and Top adsorption sites with the cyclopropane ring parallel to the surface. Pt-C equilibrium distance is ∼3.5 Å and a weak bond is formed during adsorption. The main bonding interaction comes from the Pt-H overlap population. Pt 5p z orbitals play an important role in the bonding between c-C 3 H 6 and the surface. We have found that Van der Waals (vdW) corrections to the energies improve the adsorption values without changing the preferential site geometries.

  8. Identification of surface species by vibrational normal mode analysis. A DFT study

    Science.gov (United States)

    Zhao, Zhi-Jian; Genest, Alexander; Rösch, Notker

    2017-10-01

    Infrared spectroscopy is an important experimental tool for identifying molecular species adsorbed on a metal surface that can be used in situ. Often vibrational modes in such IR spectra of surface species are assigned and identified by comparison with vibrational spectra of related (molecular) compounds of known structure, e. g., an organometallic cluster analogue. To check the validity of this strategy, we carried out a computational study where we compared the normal modes of three C2Hx species (x = 3, 4) in two types of systems, as adsorbates on the Pt(111) surface and as ligands in an organometallic cluster compound. The results of our DFT calculations reproduce the experimental observed frequencies with deviations of at most 50 cm-1. However, the frequencies of the C2Hx species in both types of systems have to be interpreted with due caution if the coordination mode is unknown. The comparative identification strategy works satisfactorily when the coordination mode of the molecular species (ethylidyne) is similar on the surface and in the metal cluster. However, large shifts are encountered when the molecular species (vinyl) exhibits different coordination modes on both types of substrates.

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  10. 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.

  11. Computational anatomy based on whole body imaging basic principles of computer-assisted diagnosis and therapy

    CERN Document Server

    Masutani, Yoshitaka

    2017-01-01

    This book deals with computational anatomy, an emerging discipline recognized in medical science as a derivative of conventional anatomy. It is also a completely new research area on the boundaries of several sciences and technologies, such as medical imaging, computer vision, and applied mathematics. Computational Anatomy Based on Whole Body Imaging highlights the underlying principles, basic theories, and fundamental techniques in computational anatomy, which are derived from conventional anatomy, medical imaging, computer vision, and applied mathematics, in addition to various examples of applications in clinical data. The book will cover topics on the basics and applications of the new discipline. Drawing from areas in multidisciplinary fields, it provides comprehensive, integrated coverage of innovative approaches to computational anatomy. As well,Computational Anatomy Based on Whole Body Imaging serves as a valuable resource for researchers including graduate students in the field and a connection with ...

  12. Computational Molecular Nanoscience Study of the Properties of Copper Complexes for Dye-Sensitized Solar Cells

    Science.gov (United States)

    Baldenebro-López, Jesús; Castorena-González, José; Flores-Holguín, Norma; Almaral-Sánchez, Jorge; Glossman-Mitnik, Daniel

    2012-01-01

    In this work, we studied a copper complex-based dye, which is proposed for potential photovoltaic applications and is named Cu (I) biquinoline dye. Results of electron affinities and ionization potentials have been used for the correlation between different levels of calculation used in this study, which are based on The Density Functional Theory (DFT) and time-dependent (TD) DFT. Further, the maximum absorption wavelengths of our theoretical calculations were compared with the experimental data. It was found that the M06/LANL2DZ + DZVP level of calculation provides the best approximation. This level of calculation was used to find the optimized molecular structure and to predict the main molecular vibrations, the molecular orbitals energies, dipole moment, isotropic polarizability and the chemical reactivity parameters that arise from Conceptual DFT. PMID:23443107

  13. Interactive Computer-Assisted Instruction in Acid-Base Physiology for Mobile Computer Platforms

    Science.gov (United States)

    Longmuir, Kenneth J.

    2014-01-01

    In this project, the traditional lecture hall presentation of acid-base physiology in the first-year medical school curriculum was replaced by interactive, computer-assisted instruction designed primarily for the iPad and other mobile computer platforms. Three learning modules were developed, each with ~20 screens of information, on the subjects…

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

    Science.gov (United States)

    Tugsuz, Tugba

    2010-12-30

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

  15. Concordance-based Kendall's Correlation for Computationally-Light vs. Computationally-Heavy Centrality Metrics: Lower Bound for Correlation

    Directory of Open Access Journals (Sweden)

    Natarajan Meghanathan

    2017-01-01

    Full Text Available We identify three different levels of correlation (pair-wise relative ordering, network-wide ranking and linear regression that could be assessed between a computationally-light centrality metric and a computationally-heavy centrality metric for real-world networks. The Kendall's concordance-based correlation measure could be used to quantitatively assess how well we could consider the relative ordering of two vertices vi and vj with respect to a computationally-light centrality metric as the relative ordering of the same two vertices with respect to a computationally-heavy centrality metric. We hypothesize that the pair-wise relative ordering (concordance-based assessment of the correlation between centrality metrics is the most strictest of all the three levels of correlation and claim that the Kendall's concordance-based correlation coefficient will be lower than the correlation coefficient observed with the more relaxed levels of correlation measures (linear regression-based Pearson's product-moment correlation coefficient and the network wide ranking-based Spearman's correlation coefficient. We validate our hypothesis by evaluating the three correlation coefficients between two sets of centrality metrics: the computationally-light degree and local clustering coefficient complement-based degree centrality metrics and the computationally-heavy eigenvector centrality, betweenness centrality and closeness centrality metrics for a diverse collection of 50 real-world networks.

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

    Science.gov (United States)

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

    2018-04-01

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

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

    Directory of Open Access Journals (Sweden)

    María Martín-Rodríguez

    2013-11-01

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

  18. DFT investigation on the adsorption behavior of dimethyl and trimethyl amine molecules on borophene nanotube

    Science.gov (United States)

    Bhuvaneswari, R.; Chandiramouli, R.

    2018-06-01

    The electronic properties of borophene nanotube (BNT) are witnessed and the adsorption properties of dimethyl amine (DMA) and trimethyl amine (TMA) molecules on borophene nanotube are explored through non-equilibrium Green's function (NEGF) and density functional theory (DFT) method. The device density of states spectrum interprets the change in peak maxima, thus indicating the electron transition between DMA, TMA molecules and BNT base material. I-V characteristics strengthen the adsorption property of DMA and TMA on BNT by pointing out the variation in the current. The present work assures that borophene nanotube (BNT) can be employed as DMA and TMA sensor.

  19. Computer-Based Simulation Games in Public Administration Education

    Directory of Open Access Journals (Sweden)

    Kutergina Evgeniia

    2017-12-01

    Full Text Available Computer simulation, an active learning technique, is now one of the advanced pedagogical technologies. Th e use of simulation games in the educational process allows students to gain a firsthand understanding of the processes of real life. Public- administration, public-policy and political-science courses increasingly adopt simulation games in universities worldwide. Besides person-to-person simulation games, there are computer-based simulations in public-administration education. Currently in Russia the use of computer-based simulation games in Master of Public Administration (MPA curricula is quite limited. Th is paper focuses on computer- based simulation games for students of MPA programmes. Our aim was to analyze outcomes of implementing such games in MPA curricula. We have done so by (1 developing three computer-based simulation games about allocating public finances, (2 testing the games in the learning process, and (3 conducting a posttest examination to evaluate the effect of simulation games on students’ knowledge of municipal finances. Th is study was conducted in the National Research University Higher School of Economics (HSE and in the Russian Presidential Academy of National Economy and Public Administration (RANEPA during the period of September to December 2015, in Saint Petersburg, Russia. Two groups of students were randomly selected in each university and then randomly allocated either to the experimental or the control group. In control groups (n=12 in HSE, n=13 in RANEPA students had traditional lectures. In experimental groups (n=12 in HSE, n=13 in RANEPA students played three simulation games apart from traditional lectures. Th is exploratory research shows that the use of computer-based simulation games in MPA curricula can improve students’ outcomes by 38 %. In general, the experimental groups had better performances on the post-test examination (Figure 2. Students in the HSE experimental group had 27.5 % better

  20. Conception of Repairable Dynamic Fault Trees and resolution by the use of RAATSS, a Matlab® toolbox based on the ATS formalism

    International Nuclear Information System (INIS)

    Manno, G.; Chiacchio, F.; Compagno, L.; D'Urso, D.; Trapani, N.

    2014-01-01

    Dynamic Fault Tree (DFT) is a well-known stochastic technique for conducting reliability studies of complex systems. At the state of the art, existing tools (both academic and commercial) do not fully support DFT with repairable components and repeated events, lowering the penetration of this powerful technique in real industrial applications (e.g., industrial processes and plants, computer, electronic and network applications). One of the main reasons limiting the attractiveness of DFT is that, originally, DFTs were conceived without repairable components; only recently few related works have started to deal with a formal semantic, which would avoid undefined behavior and misinterpretation of DFT. Other researchers have tackled the problem by introducing extensions of the original Fault Trees (FTs) technique like Boolean Driven Markov Processes (BDMPs) and Generalized Fault Trees (GFTs). However, despite they consider repairable systems and repeated events, we have found that the introduction of a different formalism with more complex features has again limited the penetration of these powerful methods in real applications. The target of this work is the original DFT technique. Starting from the state of the art, a set of standardized rules that frame the behaviors of dynamic gates are designed and a well-defined semantic for repairable-DFT is drawn through the application of a novel formalism, the Adaptive Transitions System (ATS). The proposed theoretical framework is afterward used to code a software tool, RAATSS, for the resolution of extended, repairable-DFT. Moreover, this work introduces some novel concepts regarding the modeling of a system by a DFT and provides a basic hint of the ATS capabilities to describe interdependencies in complex system. - Highlights: • A semantic for Repairable Dynamic Fault Tree (RDFT) was conceived. • Practical motivation for the use of RDFT is presented. • The conception of failure gates for the computation of the

  1. 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

  2. Game based learning for computer science education

    NARCIS (Netherlands)

    Schmitz, Birgit; Czauderna, André; Klemke, Roland; Specht, Marcus

    2011-01-01

    Schmitz, B., Czauderna, A., Klemke, R., & Specht, M. (2011). Game based learning for computer science education. In G. van der Veer, P. B. Sloep, & M. van Eekelen (Eds.), Computer Science Education Research Conference (CSERC '11) (pp. 81-86). Heerlen, The Netherlands: Open Universiteit.

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

    Directory of Open Access Journals (Sweden)

    Assem Barakat

    2016-09-01

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

  4. Electronic structure and nature of the ground state of the mixed-valence binuclear tetra(mu-1,8-naphthyridine-N,N')-bis(halogenonickel) tetraphenylborate complexes: experimental and DFT characterization.

    Science.gov (United States)

    Bencini, Alessandro; Berti, Elisabetta; Caneschi, Andrea; Gatteschi, Dante; Giannasi, Elisa; Invernizzi, Ivana

    2002-08-16

    The ground state electronic structure of the mixed-valence systems [Ni(2)(napy)(4)X(2)](BPh(4)) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence of the magnetic susceptibility, and high-field EPR spectroscopy) and theoretical (DFT) methods. The zero-field splitting (zfs) ground S=3/2 spin state is axial with /D/ approximately 3 cm(-1). The iodide derivative was found to be isostructural with the previously reported bromide complex, but not isomorphous. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on the S=3/2 state to characterize the ground state potential energy surface as a function of the nuclear displacements. The molecules can thus be classified as Class III mixed-valence compounds with a computed delocalization parameter, B=3716, 3583, and 3261 cm(-1) for the Cl, Br, and I derivatives, respectively.

  5. Room temperature ferromagnetism and half metallicity in nickel doped ZnS: Experimental and DFT studies

    Energy Technology Data Exchange (ETDEWEB)

    Akhtar, Muhammad Saeed [School of Materials, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590 (Pakistan); Malik, Mohammad Azad, E-mail: Azad.malik@manchester.ac.uk [School of Materials, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Riaz, Saira; Naseem, Shahzad [Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590 (Pakistan)

    2015-06-15

    The nickel doped nanocrystalline ZnS thin films were deposited onto glass substrates by chemical bath deposition (CBD). Also ZnS:Ni nanoparticles were synthesized by CBD/co-precipitation method. Powder X-ray diffraction (p-XRD) studies demonstrate that both thin films and nanoparticles correspond to sphalerite (cubic) phase of ZnS with slight shift towards higher 2θ values due to incorporation of nickel in the ZnS lattice. The crystallite sizes estimated by Scherrer equation were 4 and 2.6 nm for ZnNiS thin films and nanoparticles, respectively. Scanning Electron Microscopy (SEM) images reveal that the morphology of thin films is based on quasi-spherical particles with nano scale dimensions. Energy Dispersive X-ray (EDX) spectroscopy confirms that the as-deposited thin films have a stoichiometry consistent with the nickel doped ZnS. Full-potential linearized augmented plane wave (FP-L/APW) method based on spin-polarized density functional theory (DFT) was employed to investigate the electronic and magnetic properties of ZnNiS for the doping concentration. Exchange-correlation functional was studied using generalized gradient approximation (GGA + U) method. Electronic band structures and density of states (DOS) demonstrate 100% spin polarization (half metallicity) with ferromagnetic exchange interactions. Superconducting quantum interference device (SQUID) analysis confirms the theoretical observation of ferromagnetism in nickel doped ZnS. These ZnS based half metallic ferromagnets seem to have virtuous applications in future spintronic devices. - Highlights: • ZnS.Ni thin films and nanoparticles were deposited onto glass substrates by CBD. • p-XRD correspond to sphalerite (cubic) phase of ZnS with slight shift in peaks. • DFT was employed to investigate the properties of ZnS.Ni. • DOS demonstrate 100% spin polarization with ferromagnetic exchange interactions. • SQUID analysis confirms the theoretical observations of nickel doped ZnS.

  6. 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.

  7. Women and Computer Based Technologies: A Feminist Perspective.

    Science.gov (United States)

    Morritt, Hope

    The use of computer based technologies by professional women in education is examined through a feminist standpoint theory in this paper. The theory is grounded in eight claims which form the basis of the conceptual framework for the study. The experiences of nine women participants with computer based technologies were categorized using three…

  8. Spectro-electrochemical and DFT study of tenoxicam metabolites formed by electrochemical oxidation

    International Nuclear Information System (INIS)

    Ramírez-Silva, M.T.; Guzmán-Hernández, D.S.; Galano, A.; Rojas-Hernández, A.; Corona-Avendaño, S.; Romero-Romo, M.; Palomar-Pardavé, M.

    2013-01-01

    Highlights: • Tenoxicam deprotonation and electrochemical oxidation were studied. • Both spectro-electrochemical and theoretical DFT studies were considered. • It was found that the ampholitic species of tenoxicam is a zwitterion. • Electrochemical oxidation of tenoxicam yields two non-electroactive products. • The nature of these fragments was further confirmed by a chromatography study. -- Abstract: From experimental (spectro-electrochemical) and theoretical (DFT) studies, the mechanisms of tenoxicam deprotonation and electrochemical oxidation were assessed. From these studies, new insights on the nature of the ampholitic species involved during tenoxicam's deprotonation in aqueous solution are presented; see scheme A. Moreover, it is shown that, after the analysis of two different reaction schemes that involve up to 10 different molecules and 12 reaction paths, the electrochemical oxidation of tenoxicam, yields two non-electroactive products that are predominately formed by its fragmentation, after the loss of two electrons. The nature of these fragments was further confirmed by a chromatography study

  9. Effect of organic molecules on hydrolysis of peptide bond: A DFT study

    International Nuclear Information System (INIS)

    Makshakova, Olga; Ermakova, Elena

    2013-01-01

    Highlights: ► DFT study of the effects of small organic molecules on the hydrolysis reactions of peptide bonds. ► Organic molecules can activate nonenzymatic hydrolysis reaction. ► Influence of organic acids on activation energy barrier correlates with their electronegativity. - Abstract: The activation and inhibition effects of small organic molecules on peptide hydrolysis have been studied using a model compound dialanine and DFT approach. Solvent-assisted and non-assisted concerted mechanisms were analyzed. Several transition states for the systems: alanine dipeptide–water molecule in complexes with alcohol molecules, acetonitrile, dimethylsulfoxide, propionic, lactic and pyruvic acids and water molecules were localized. The formation of hydrogen bonds between dipeptide, reactive water molecule and molecules of solvents influences the activation energy barrier of the peptide bond hydrolytic reaction. Strong effect of organic acids on the activation energy barrier correlates with their electronegativity. Acetonitrile can act as an inhibitor of reaction. Mechanisms of regulation of the activation energy barrier are discussed in the terms of donor-acceptor interactions

  10. DFT Perspective on the Thermochemistry of Carbon Nitride Synthesis

    KAUST Repository

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

    2016-01-01

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

  11. DFT Perspective on the Thermochemistry of Carbon Nitride Synthesis

    KAUST Repository

    Melissen, Sigismund T. A. G.

    2016-10-11

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

  12. A DFT Structural Investigation of New Bimetallic PtSnx Surface Alloys Formed on the Pt(110) Surface and Their Interaction with Carbon Monoxide

    DEFF Research Database (Denmark)

    Zheng, Jian; Busch, Michael; Artiglia, Luca

    2016-01-01

    desorbs from the PtSnx surfaces at about 415-425 K compared to 495 K on the clean Pt(110). The energetics and geometry of the CO chemisorption sites have been studied by DFT calculations, obtaining an adsorption energy of 0.7-0.86 eV on p(3 x 1) and 0.9-1.05 eV on p(6 x 1). Overall our theoretical...... spectroscopy. Based on the experimental results and density functional theory (DFT) calculations, we propose atomic models for these surface alloys, which both consist of a highly corrugated row structure with a very similar surface motif. CO temperature-programmed desorption (TPD) experiments indicate that CO...

  13. Discrete Fourier transformation processor based on complex radix (−1 + j number system

    Directory of Open Access Journals (Sweden)

    Anidaphi Shadap

    2017-02-01

    Full Text Available Complex radix (−1 + j allows the arithmetic operations of complex numbers to be done without treating the divide and conquer rules, which offers the significant speed improvement of complex numbers computation circuitry. Design and hardware implementation of complex radix (−1 + j converter has been introduced in this paper. Extensive simulation results have been incorporated and an application of this converter towards the implementation of discrete Fourier transformation (DFT processor has been presented. The functionality of the DFT processor have been verified in Xilinx ISE design suite version 14.7 and performance parameters like propagation delay and dynamic switching power consumption have been calculated by Virtuoso platform in Cadence. The proposed DFT processor has been implemented through conversion, multiplication and addition. The performance parameter matrix in terms of delay and power consumption offered a significant improvement over other traditional implementation of DFT processor.

  14. An overview of computer-based natural language processing

    Science.gov (United States)

    Gevarter, W. B.

    1983-01-01

    Computer based Natural Language Processing (NLP) is the key to enabling humans and their computer based creations to interact with machines in natural language (like English, Japanese, German, etc., in contrast to formal computer languages). The doors that such an achievement can open have made this a major research area in Artificial Intelligence and Computational Linguistics. Commercial natural language interfaces to computers have recently entered the market and future looks bright for other applications as well. This report reviews the basic approaches to such systems, the techniques utilized, applications, the state of the art of the technology, issues and research requirements, the major participants and finally, future trends and expectations. It is anticipated that this report will prove useful to engineering and research managers, potential users, and others who will be affected by this field as it unfolds.

  15. Strategic Planning for Computer-Based Educational Technology.

    Science.gov (United States)

    Bozeman, William C.

    1984-01-01

    Offers educational practitioners direction for the development of a master plan for the implementation and application of computer-based educational technology by briefly examining computers in education, discussing organizational change from a theoretical perspective, and presenting an overview of the planning strategy known as the planning and…

  16. HuRECA: Human Reliability Evaluator for Computer-based Control Room Actions

    International Nuclear Information System (INIS)

    Kim, Jae Whan; Lee, Seung Jun; Jang, Seung Cheol

    2011-01-01

    As computer-based design features such as computer-based procedures (CBP), soft controls (SCs), and integrated information systems are being adopted in main control rooms (MCR) of nuclear power plants, a human reliability analysis (HRA) method capable of dealing with the effects of these design features on human reliability is needed. From the observations of human factors engineering verification and validation experiments, we have drawn some major important characteristics on operator behaviors and design-related influencing factors (DIFs) from the perspective of human reliability. Firstly, there are new DIFs that should be considered in developing an HRA method for computer-based control rooms including especially CBP and SCs. In the case of the computer-based procedure rather than the paper-based procedure, the structural and managerial elements should be considered as important PSFs in addition to the procedural contents. In the case of the soft controllers, the so-called interface management tasks (or secondary tasks) should be reflected in the assessment of human error probability. Secondly, computer-based control rooms can provide more effective error recovery features than conventional control rooms. Major error recovery features for computer-based control rooms include the automatic logic checking function of the computer-based procedure and the information sharing feature of the general computer-based designs

  17. Techniques for computing the discrete Fourier transform using the quadratic residue Fermat number systems

    Science.gov (United States)

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

    1986-01-01

    The complex integer multiplier and adder over the direct sum of two copies of finite field developed by Cozzens and Finkelstein (1985) is specialized to the direct sum of the rings of integers modulo Fermat numbers. Such multiplication over the rings of integers modulo Fermat numbers can be performed by means of two integer multiplications, whereas the complex integer multiplication requires three integer multiplications. Such multiplications and additions can be used in the implementation of a discrete Fourier transform (DFT) of a sequence of complex numbers. The advantage of the present approach is that the number of multiplications needed to compute a systolic array of the DFT can be reduced substantially. The architectural designs using this approach are regular, simple, expandable and, therefore, naturally suitable for VLSI implementation.

  18. 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.

  19. An introduction to statistical computing a simulation-based approach

    CERN Document Server

    Voss, Jochen

    2014-01-01

    A comprehensive introduction to sampling-based methods in statistical computing The use of computers in mathematics and statistics has opened up a wide range of techniques for studying otherwise intractable problems.  Sampling-based simulation techniques are now an invaluable tool for exploring statistical models.  This book gives a comprehensive introduction to the exciting area of sampling-based methods. An Introduction to Statistical Computing introduces the classical topics of random number generation and Monte Carlo methods.  It also includes some advanced met

  20. SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

    Science.gov (United States)

    Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

    2017-10-01

    SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.

  1. From Mahan excitons to Landau levels at high magnetic fields: 2DFT spectroscopy reveals hidden quantum correlations (Conference Presentation)

    Science.gov (United States)

    Karaiskaj, Denis

    2017-02-01

    Two-dimensional electron gases have been the subject of research for decades. Modulation doped GaAs quantum wells in the absence of magnetic fields exhibit interesting many-body physics such as the Fermi edge singularity or Mahan exciton and can be regarded as a collective excitation of the system. Under high magnetic fields Landau levels form which have been studied using transport and optical measurements. Nonlinear coherent two-dimensional Fourier transform (2DFT) spectroscopy however provides new insights into these systems. We present the 2DFT spectra of Mahan Excitons associated with the heavy-hole and light-hole resonances observed in a modulation doped GaAs/AlGaAs single quantum well [1]. These resonances are observed to be strongly coupled through many-body interactions. The 2DFT spectra were measured using co-linear, cross-linear, and co-circular polarizations and reveal striking differences. Furthermore, 2DFT spectra at high magnetic fields performed at the National High Magnetic Field Lab (NHMFL) in Tallahassee, Florida will be discussed. The spectra exhibit new features and peculiar line shapes suggesting interesting underlying physics. [1] J. Paul, C. E. Stevens, C. Liu, P. Dey, C. McIntyre, V. Turkowski, J. L. Reno, D. J. Hilton, and D. Karaiskaj, Phys. Rev. Lett.116, 157401 (2016).

  2. Computer Based Modelling and Simulation

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 3. Computer Based Modelling and Simulation - Modelling Deterministic Systems. N K Srinivasan. General Article Volume 6 Issue 3 March 2001 pp 46-54. Fulltext. Click here to view fulltext PDF. Permanent link:

  3. Molecular hyperpolarizabilities of push–pull chromophores: A comparison between theoretical and experimental results

    Energy Technology Data Exchange (ETDEWEB)

    Capobianco, A. [Dipartimento di Fisica E.R. Caianiello, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy); Centore, R. [Dipartimento di Chimica P. Corradini, Università di Napoli, via Cintia, I-80126 Napoli (Italy); Noce, C. [Dipartimento di Fisica E.R. Caianiello, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy); Peluso, A., E-mail: apeluso@unisa.it [Dipartimento di Chimica e Biologia, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy)

    2013-01-16

    Highlights: ► Electro-optical determined and MP2/DFT computed NLO properties have been compared. ► Significant dependence of dipole moments of elongated NLO chromophores on conformations has been found. ► A thorough comparison between MP2 and DFT/TD-DFT computational approaches has been carried out. ► The two-state model overestimates hyperpolarizability. - Abstract: Electric dipole moments and static first order hyperpolarizabilities of two push–pull molecules with an extended π electron systems have been evaluated at different computational levels and compared with the results of electro-optical absorption measurements, based on the two state model. Calculations show that: (i) the dipole moments of such elongated systems depend significantly on conformation, a thorough conformational search is necessary for a meaningful comparison between theoretical and experimental results; (ii) DFT methods, in particular CAM-B3LYP and M05-2X, yield dipole moments which compare well with those obtained by post Hartree–Fock methods (MP2) and by EOA measurements; (iii) theoretical first order hyperpolarizabilities are largely underestimated, both by MP2 and DFT methods, possibly because of the failure of two state model used in electro-optical measurements.

  4. Reciprocity in computer-human interaction: source-based, norm-based, and affect-based explanations.

    Science.gov (United States)

    Lee, Seungcheol Austin; Liang, Yuhua Jake

    2015-04-01

    Individuals often apply social rules when they interact with computers, and this is known as the Computers Are Social Actors (CASA) effect. Following previous work, one approach to understand the mechanism responsible for CASA is to utilize computer agents and have the agents attempt to gain human compliance (e.g., completing a pattern recognition task). The current study focuses on three key factors frequently cited to influence traditional notions of compliance: evaluations toward the source (competence and warmth), normative influence (reciprocity), and affective influence (mood). Structural equation modeling assessed the effects of these factors on human compliance with computer request. The final model shows that norm-based influence (reciprocity) increased the likelihood of compliance, while evaluations toward the computer agent did not significantly influence compliance.

  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. Computer vision based room interior design

    Science.gov (United States)

    Ahmad, Nasir; Hussain, Saddam; Ahmad, Kashif; Conci, Nicola

    2015-12-01

    This paper introduces a new application of computer vision. To the best of the author's knowledge, it is the first attempt to incorporate computer vision techniques into room interior designing. The computer vision based interior designing is achieved in two steps: object identification and color assignment. The image segmentation approach is used for the identification of the objects in the room and different color schemes are used for color assignment to these objects. The proposed approach is applied to simple as well as complex images from online sources. The proposed approach not only accelerated the process of interior designing but also made it very efficient by giving multiple alternatives.

  8. Agent-Based Computing: Promise and Perils

    OpenAIRE

    Jennings, N. R.

    1999-01-01

    Agent-based computing represents an exciting new synthesis both for Artificial Intelligence (AI) and, more genrally, Computer Science. It has the potential to significantly improve the theory and practice of modelling, designing and implementing complex systems. Yet, to date, there has been little systematic analysis of what makes an agent such an appealing and powerful conceptual model. Moreover, even less effort has been devoted to exploring the inherent disadvantages that stem from adoptin...

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

    Directory of Open Access Journals (Sweden)

    Śmiszek-Lindert Wioleta

    2015-01-01

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

  10. Semi-Local DFT Functionals with Exact-Exchange-Like Features: Beyond the AK13

    Science.gov (United States)

    Armiento, Rickard

    The Armiento-Kümmel functional from 2013 (AK13) is a non-empirical semi-local exchange functional on generalized gradient approximation form (GGA) in Kohn-Sham (KS) density functional theory (DFT). Recent works have established that AK13 gives improved electronic-structure exchange features over other semi-local methods, with a qualitatively improved orbital description and band structure. For example, the Kohn-Sham band gap is greatly extended, as it is for exact exchange. This talk outlines recent efforts towards new exchange-correlation functionals based on, and extending, the AK13 design ideas. The aim is to improve the quantitative accuracy, the description of energetics, and to address other issues found with the original formulation. Swedish e-Science Research Centre (SeRC).

  11. Computer-Based Interaction Analysis with DEGREE Revisited

    Science.gov (United States)

    Barros, B.; Verdejo, M. F.

    2016-01-01

    We review our research with "DEGREE" and analyse how our work has impacted the collaborative learning community since 2000. Our research is framed within the context of computer-based interaction analysis and the development of computer-supported collaborative learning (CSCL) tools. We identify some aspects of our work which have been…

  12. A new multifunctional 1, 10-phenanthroline based fluorophore for anion and cation sensing

    Energy Technology Data Exchange (ETDEWEB)

    Alreja, Priya; Kaur, Navneet, E-mail: neet_chem@yahoo.co.in

    2015-12-15

    We report a new multi-ion responsive fluorophore 1 possessing an amide functionality featuring with 1, 10-phenanthroline unit with appropriately placed coordination sites for sensing Cu{sup 2+} and Zn{sup 2+} ions in 1:2 stoichiometry. Also, various functionalities of 1 organize to create an appropriate cavity to accommodate weakly basic and larger iodide ion generating 1:1 complex. The fluorescence intensity was greatly quenched on coordination of Cu{sup 2+}, Zn{sup 2+} and I{sup −} ions with appropriately placed multiple donor sites of 1 which was further supported by Density Functional Theory (DFT) computational studies. - Highlights: • A novel multifunctional 1, 10- Phenanthroline based fluorophore for sensing anion and cations. • First report on applicability of amides as multiple users for anion and cations. • Fluorescence quenching observed with Cu{sup 2+}, Zn{sup 2+} and I{sup -}. • Fluorescence titration experiments are well supported by DFT calculations.

  13. The solvent effects on dimethyl phthalate investigated by FTIR characterization, solvent parameter correlation and DFT computation

    Science.gov (United States)

    Chen, Yi; Zhang, Hui; Zhou, Wenzhao; Deng, Chao; Liao, Jian

    2018-06-01

    This study set out with the aim of investigating the solvent effects on dimethyl phthalate (DMP) using FTIR characterization, solvent parameter correlation and DFT calculation. DMP exposed to 17 organic solvents manifested varying shift in the carbonyl stretching vibration frequency (νCdbnd O). Non-alkanols induced Band I and alkanols produced Band I and Band II. Through correlating the νCdbnd O with the empirical solvent scales including acceptor parameter (AN), Schleyer's linear free energy parameter (G), and linear free salvation energy relationships (LSER), Band I was mainly ascribed to non-specific effects from either non-alkanols or alkanol polymers ((alkanol)n). νCdbnd O of the latter indicated minor red shift and less variability compared to the former. An assumption was made and validated about the sequestering of hydroxyl group by the bulky hydrophobic chain in (alkanol)n, creating what we refer to as "screening effects". Ab initio calculation, on the other hand, provided insights for possible hydrogen binding between DMP and (ethanol)n or between ethanol monomers. The two components of Band I observed in inert solvents were assigned to the two Cdbnd O groups adopting differentiated conformations. This in turn prompted our consideration that hydrogen binding was highly selective in favor of lowly associated (alkanol)n and the particular Cdbnd O group having relatively less steric hindrance and stronger electron-donating capacity. Band II was therefore believed to derive from hydrogen-bond interactions mainly in manner of 1:1 and 1:2 DMP-(alkanol)n complexes.

  14. 26 CFR 1.809-10 - Computation of equity base.

    Science.gov (United States)

    2010-04-01

    ... 26 Internal Revenue 8 2010-04-01 2010-04-01 false Computation of equity base. 1.809-10 Section 1... (CONTINUED) INCOME TAXES Gain and Loss from Operations § 1.809-10 Computation of equity base. (a) In general. For purposes of section 809, the equity base of a life insurance company includes the amount of any...

  15. DFT+U study of self-trapping, trapping, and mobility of oxygen-type hole polarons in barium stannate

    Science.gov (United States)

    Geneste, Grégory; Amadon, Bernard; Torrent, Marc; Dezanneau, Guilhem

    2017-10-01

    The charge-transfer insulating perovskite oxides currently used as fuel cell electrolytes undergo, at high temperature, an oxidation reaction 1/2 O2(g ) +VO••→OOX+2 h• , that produces oxygen-type holes. Understanding the nature and mobility of these oxygen-type holes is an important step to improve the performance of devices, but presents a theoretical challenge since, in their localized form, they cannot be captured by standard density functional theory. Here, we employ the DFT+U formalism with a Hubbard correction on the p orbitals of oxygen to investigate several properties of these holes, in the particular case of BaSnO3. We describe the small oxygen-type hole polarons, the self-trapping at their origin, and their trapping by trivalent dopants (Ga, Sc, In, Lu, Y, Gd, La). Strong similarities with protonic defects are observed concerning the evolution of the trapping energy with ionic radius of the dopant. Moreover, we show that long-range diffusion of holes is a complex phenomenon, that proceeds by a succession of several mechanisms. However, the standard implementation of DFT+U within the projector augmented-wave (PAW) formalism leads to use very large, unphysical values of U for the O-p orbital. We propose here a slightly modified DFT+U scheme, that takes into account the fact that the O-p is truncated in usual DFT+U implementation in PAW. This scheme yields more physical values of U than the ones traditionally used in the literature, and describes well the properties of the hole polaron.

  16. Enhancing Lecture Presentations in Introductory Biology with Computer-Based Multimedia.

    Science.gov (United States)

    Fifield, Steve; Peifer, Rick

    1994-01-01

    Uses illustrations and text to discuss convenient ways to organize and present computer-based multimedia to students in lecture classes. Includes the following topics: (1) Effects of illustrations on learning; (2) Using computer-based illustrations in lecture; (3) MacPresents-Multimedia Presentation Software; (4) Advantages of computer-based…

  17. Remote media vision-based computer input device

    Science.gov (United States)

    Arabnia, Hamid R.; Chen, Ching-Yi

    1991-11-01

    In this paper, we introduce a vision-based computer input device which has been built at the University of Georgia. The user of this system gives commands to the computer without touching any physical device. The system receives input through a CCD camera; it is PC- based and is built on top of the DOS operating system. The major components of the input device are: a monitor, an image capturing board, a CCD camera, and some software (developed by use). These are interfaced with a standard PC running under the DOS operating system.

  18. High-throughput computational search for strengthening precipitates in alloys

    International Nuclear Information System (INIS)

    Kirklin, S.; Saal, James E.; Hegde, Vinay I.; Wolverton, C.

    2016-01-01

    The search for high-strength alloys and precipitation hardened systems has largely been accomplished through Edisonian trial and error experimentation. Here, we present a novel strategy using high-throughput computational approaches to search for promising precipitate/alloy systems. We perform density functional theory (DFT) calculations of an extremely large space of ∼200,000 potential compounds in search of effective strengthening precipitates for a variety of different alloy matrices, e.g., Fe, Al, Mg, Ni, Co, and Ti. Our search strategy involves screening phases that are likely to produce coherent precipitates (based on small lattice mismatch) and are composed of relatively common alloying elements. When combined with the Open Quantum Materials Database (OQMD), we can computationally screen for precipitates that either have a stable two-phase equilibrium with the host matrix, or are likely to precipitate as metastable phases. Our search produces (for the structure types considered) nearly all currently known high-strength precipitates in a variety of fcc, bcc, and hcp matrices, thus giving us confidence in the strategy. In addition, we predict a number of new, currently-unknown precipitate systems that should be explored experimentally as promising high-strength alloy chemistries.

  19. Inversion based on computational simulations

    International Nuclear Information System (INIS)

    Hanson, K.M.; Cunningham, G.S.; Saquib, S.S.

    1998-01-01

    A standard approach to solving inversion problems that involve many parameters uses gradient-based optimization to find the parameters that best match the data. The authors discuss enabling techniques that facilitate application of this approach to large-scale computational simulations, which are the only way to investigate many complex physical phenomena. Such simulations may not seem to lend themselves to calculation of the gradient with respect to numerous parameters. However, adjoint differentiation allows one to efficiently compute the gradient of an objective function with respect to all the variables of a simulation. When combined with advanced gradient-based optimization algorithms, adjoint differentiation permits one to solve very large problems of optimization or parameter estimation. These techniques will be illustrated through the simulation of the time-dependent diffusion of infrared light through tissue, which has been used to perform optical tomography. The techniques discussed have a wide range of applicability to modeling including the optimization of models to achieve a desired design goal

  20. 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

  1. A quantum computer based on recombination processes in microelectronic devices

    International Nuclear Information System (INIS)

    Theodoropoulos, K; Ntalaperas, D; Petras, I; Konofaos, N

    2005-01-01

    In this paper a quantum computer based on the recombination processes happening in semiconductor devices is presented. A 'data element' and a 'computational element' are derived based on Schokley-Read-Hall statistics and they can later be used to manifest a simple and known quantum computing process. Such a paradigm is shown by the application of the proposed computer onto a well known physical system involving traps in semiconductor devices

  2. "Transit data"-based MST computation

    Directory of Open Access Journals (Sweden)

    Thodoris Karatasos

    2017-10-01

    Full Text Available In this work, we present an innovative image recognition technique which is based on the exploitation of transit-data in images or simple photographs of sites of interest. Our objective is to automatically transform real-world images to graphs and, then, compute Minimum Spanning Trees (MST in them.We apply this framework and present an application which automatically computes efficient construction plans (for escalator or low-emission hot spots for connecting all points of interest in cultural sites, i.e., archaeological sites, museums, galleries, etc, aiming to to facilitate global physical access to cultural heritage and artistic work and make it accessible to all groups of population.

  3. Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction

    DEFF Research Database (Denmark)

    Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.

    2008-01-01

    Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole...

  4. Standardized computer-based organized reporting of EEG:SCORE

    DEFF Research Database (Denmark)

    Beniczky, Sandor; H, Aurlien,; JC, Brøgger,

    2013-01-01

    process, organized by the European Chapter of the International Federation of Clinical Neurophysiology. The Standardised Computer-based Organised Reporting of EEG (SCORE) software was constructed based on the terms and features of the consensus statement and it was tested in the clinical practice...... in free-text format. The purpose of our endeavor was to create a computer-based system for EEG assessment and reporting, where the physicians would construct the reports by choosing from predefined elements for each relevant EEG feature, as well as the clinical phenomena (for video-EEG recordings....... SCORE can potentially improve the quality of EEG assessment and reporting; it will help incorporate the results of computer-assisted analysis into the report, it will make possible the build-up of a multinational database, and it will help in training young neurophysiologists....

  5. 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.

  6. 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.

  7. Computer Based Road Accident Reconstruction Experiences

    Directory of Open Access Journals (Sweden)

    Milan Batista

    2005-03-01

    Full Text Available Since road accident analyses and reconstructions are increasinglybased on specific computer software for simulationof vehicle d1iving dynamics and collision dynamics, and forsimulation of a set of trial runs from which the model that bestdescribes a real event can be selected, the paper presents anoverview of some computer software and methods available toaccident reconstruction experts. Besides being time-saving,when properly used such computer software can provide moreauthentic and more trustworthy accident reconstruction, thereforepractical experiences while using computer software toolsfor road accident reconstruction obtained in the TransportSafety Laboratory at the Faculty for Maritime Studies andTransport of the University of Ljubljana are presented and discussed.This paper addresses also software technology for extractingmaximum information from the accident photo-documentationto support accident reconstruction based on the simulationsoftware, as well as the field work of reconstruction expertsor police on the road accident scene defined by this technology.

  8. What Density Functional Theory could do for Quantum Information

    Science.gov (United States)

    Mattsson, Ann

    2015-03-01

    The Hohenberg-Kohn theorem of Density Functional Theory (DFT), and extensions thereof, tells us that all properties of a system of electrons can be determined through their density, which uniquely determines the many-body wave-function. Given access to the appropriate, universal, functionals of the density we would, in theory, be able to determine all observables of any electronic system, without explicit reference to the wave-function. On the other hand, the wave-function is at the core of Quantum Information (QI), with the wave-function of a set of qubits being the central computational resource in a quantum computer. While there is seemingly little overlap between DFT and QI, reliance upon observables form a key connection. Though the time-evolution of the wave-function and associated phase information is fundamental to quantum computation, the initial and final states of a quantum computer are characterized by observables of the system. While observables can be extracted directly from a system's wave-function, DFT tells us that we may be able to intuit a method for extracting them from its density. In this talk, I will review the fundamentals of DFT and how these principles connect to the world of QI. This will range from DFT's utility in the engineering of physical qubits, to the possibility of using it to efficiently (but approximately) simulate Hamiltonians at the logical level. The apparent paradox of describing algorithms based on the quantum mechanical many-body wave-function with a DFT-like theory based on observables will remain a focus throughout. The ultimate goal of this talk is to initiate a dialog about what DFT could do for QI, in theory and in practice. 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-AC04-94AL85000.

  9. 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.

  10. Synthesis, structure and DFT conformation analysis of CpNiX(NHC) and NiX2(NHC)2 (X = SPh or Br) complexes

    Science.gov (United States)

    Malan, Frederick P.; Singleton, Eric; van Rooyen, Petrus H.; Conradie, Jeanet; Landman, Marilé

    2017-11-01

    The synthesis, density functional theory (DFT) conformational study and structure analysis of novel two-legged piano stool Ni N-heterocyclic carbene (NHC) complexes and square planar Ni bis-N-heterocyclic carbene complexes, all containing either bromido- or thiophenolato ligands, are described. [CpNi(SPh)(NHC)] complexes were obtained from the neutral 18-electron [CpNiBr(NHC)] complexes by substitution of a bromido ligand with SPh, using NEt3 as a base to abstract the proton of HSPh. The 16-electron biscarbene complexes [Ni(SPh)2{NHC}2] were isolated when an excess of HSPh was added to the reaction mixture. Biscarbene complexes of the type [NiBr2(NHC)2] were obtained in the reaction of NiCp2 with a slight excess of the specific imidazolium bromide salt. The molecular and electronic structures of the mono- and bis-N-heterocyclic carbene complexes have been analysed using single crystal diffraction and density functional theory (DFT) calculations, to give insight into their structural properties.

  11. 3D-FT MRI of the facial nerve

    International Nuclear Information System (INIS)

    Girard, N.; Raybaud, C.; Poncet, M.

    1994-01-01

    Contrast-enhanced 3D-FT MRI of the intrapetrous facial nerve was obtained in 38 patients with facial nerve disease, using a 1.0 T magnet and fast gradient-echo acquisition sequences. Contiguous millimetric sections were obtained, which could be reformatted in any desired plane. Acutely ill patients, were examined within the first 2 months, included: 24 with Bell's palsy and 6 with other acute disorders (Herpes zoster, trauma, neuroma, meningeal metastasis, middle ear granuloma). Six patients investigated more than a year after the onset of symptoms included 3 with congenital cholesteatoma, 2 with neuromas and one with a chronic Bell's palsy. The lesion was found incidentally in two cases (a suspected neurofibroma and a presumed drop metastasis from an astrocytoma). Patients with tumours had nodular, focally-enhancing lesions, except for the leptomeningeal metastasis in which the enhancement was linear. Linear, diffuse contrast enhancement of the facial nerve was found in trauma, and in the patient with a middle ear granuloma. Of the 24 patients with an acute Bell's palsy 15 exhibited linear contrast enhancement of the facial nerve. Three of these were lost to follow-up, but correlation of clinical outcome and contrast enhancement showed that only 4 of the 11 patients who made a complete recovery and all 10 patients with incomplete recovery demonstrated enhancement. Possible explanations for these findings are suggested by pathological data from the literature. 3D-FT imaging of the facial nerve thus yields direct information about the of the nerve condition and defines the morphological abnormalities. It can also demonstrate contrast enhancement which seems to have some prognostic value in acute idiopathic Bell's palsy. (orig.)

  12. Standardized computer-based organized reporting of EEG

    DEFF Research Database (Denmark)

    Beniczky, Sándor; Aurlien, Harald; Brøgger, Jan C.

    2017-01-01

    Standardized terminology for computer-based assessment and reporting of EEG has been previously developed in Europe. The International Federation of Clinical Neurophysiology established a taskforce in 2013 to develop this further, and to reach international consensus. This work resulted in the se......Standardized terminology for computer-based assessment and reporting of EEG has been previously developed in Europe. The International Federation of Clinical Neurophysiology established a taskforce in 2013 to develop this further, and to reach international consensus. This work resulted...... in the second, revised version of SCORE (Standardized Computer-based Organized Reporting of EEG), which is presented in this paper. The revised terminology was implemented in a software package (SCORE EEG), which was tested in clinical practice on 12,160 EEG recordings. Standardized terms implemented in SCORE....... In the end, the diagnostic significance is scored, using a standardized list of terms. SCORE has specific modules for scoring seizures (including seizure semiology and ictal EEG patterns), neonatal recordings (including features specific for this age group), and for Critical Care EEG Terminology. SCORE...

  13. Standardized computer-based organized reporting of EEG

    DEFF Research Database (Denmark)

    Beniczky, Sándor; Aurlien, Harald; Brøgger, Jan C.

    2017-01-01

    Standardized terminology for computer-based assessment and reporting of EEG has been previously developed in Europe. The International Federation of Clinical Neurophysiology established a taskforce in 2013 to develop this further, and to reach international consensus. This work resulted in the se......Standardized terminology for computer-based assessment and reporting of EEG has been previously developed in Europe. The International Federation of Clinical Neurophysiology established a taskforce in 2013 to develop this further, and to reach international consensus. This work resulted...... in the second, revised version of SCORE (Standardized Computer-based Organized Reporting of EEG), which is presented in this paper. The revised terminology was implemented in a software package (SCORE EEG), which was tested in clinical practice on 12,160 EEG recordings. Standardized terms implemented in SCORE...... are used to report the features of clinical relevance, extracted while assessing the EEGs. Selection of the terms is context sensitive: initial choices determine the subsequently presented sets of additional choices. This process automatically generates a report and feeds these features into a database...

  14. A Weibull-based compositional approach for hierarchical dynamic fault trees

    International Nuclear Information System (INIS)

    Chiacchio, F.; Cacioppo, M.; D'Urso, D.; Manno, G.; Trapani, N.; Compagno, L.

    2013-01-01

    The solution of a dynamic fault tree (DFT) for the reliability assessment can be achieved using a wide variety of techniques. These techniques have a strong theoretical foundation as both the analytical and the simulation methods have been extensively developed. Nevertheless, they all present the same limits that appear with the increasing of the size of the fault trees (i.e., state space explosion, time-consuming simulations), compromising the resolution. We have tested the feasibility of a composition algorithm based on a Weibull distribution, addressed to the resolution of a general class of dynamic fault trees characterized by non-repairable basic events and generally distributed failure times. The proposed composition algorithm is used to generalize the traditional hierarchical technique that, as previous literature have extensively confirmed, is able to reduce the computational effort of a large DFT through the modularization of independent parts of the tree. The results of this study are achieved both through simulation and analytical techniques, thus confirming the capability to solve a quite general class of dynamic fault trees and overcome the limits of traditional techniques.

  15. Graphics processing unit based computation for NDE applications

    Science.gov (United States)

    Nahas, C. A.; Rajagopal, Prabhu; Balasubramaniam, Krishnan; Krishnamurthy, C. V.

    2012-05-01

    Advances in parallel processing in recent years are helping to improve the cost of numerical simulation. Breakthroughs in Graphical Processing Unit (GPU) based computation now offer the prospect of further drastic improvements. The introduction of 'compute unified device architecture' (CUDA) by NVIDIA (the global technology company based in Santa Clara, California, USA) has made programming GPUs for general purpose computing accessible to the average programmer. Here we use CUDA to develop parallel finite difference schemes as applicable to two problems of interest to NDE community, namely heat diffusion and elastic wave propagation. The implementations are for two-dimensions. Performance improvement of the GPU implementation against serial CPU implementation is then discussed.

  16. A personal computer-based nuclear magnetic resonance spectrometer

    Science.gov (United States)

    Job, Constantin; Pearson, Robert M.; Brown, Michael F.

    1994-11-01

    Nuclear magnetic resonance (NMR) spectroscopy using personal computer-based hardware has the potential of enabling the application of NMR methods to fields where conventional state of the art equipment is either impractical or too costly. With such a strategy for data acquisition and processing, disciplines including civil engineering, agriculture, geology, archaeology, and others have the possibility of utilizing magnetic resonance techniques within the laboratory or conducting applications directly in the field. Another aspect is the possibility of utilizing existing NMR magnets which may be in good condition but unused because of outdated or nonrepairable electronics. Moreover, NMR applications based on personal computer technology may open up teaching possibilities at the college or even secondary school level. The goal of developing such a personal computer (PC)-based NMR standard is facilitated by existing technologies including logic cell arrays, direct digital frequency synthesis, use of PC-based electrical engineering software tools to fabricate electronic circuits, and the use of permanent magnets based on neodymium-iron-boron alloy. Utilizing such an approach, we have been able to place essentially an entire NMR spectrometer console on two printed circuit boards, with the exception of the receiver and radio frequency power amplifier. Future upgrades to include the deuterium lock and the decoupler unit are readily envisioned. The continued development of such PC-based NMR spectrometers is expected to benefit from the fast growing, practical, and low cost personal computer market.

  17. Comparability of Computer-based and Paper-based Versions of Writing Section of PET in Iranian EFL Context

    Directory of Open Access Journals (Sweden)

    Mohammad Mohammadi

    2010-11-01

    Full Text Available Computer technology has provided language testing experts with opportunity to develop computerized versions of traditional paper-based language tests. New generations of TOEFL and Cambridge IELTS, BULATS, KET, PET are good examples of computer-based language tests. Since this new method of testing introduces new factors into the realm of language assessment ( e.g. modes of test delivery, familiarity with computer, etc.,the question may be whether the two modes of computer- and paper-based tests comparably measure the same construct, and hence, the scores obtained from the two modes can be used interchangeably. Accordingly, the present study aimed to investigate the comparability of the paper- and computer-based versions of a writing test. The data for this study were collected from administering the writing section of a Cambridge Preliminary English Test (PET to eighty Iranian intermediate EFL learners through the two modes of computer- and paper-based testing. Besides, a computer familiarity questionnaire was used to divide participants into two groups with high and low computer familiarity. The results of the independent samples t-test revealed that there was no statistically significant difference between the learners' computer- and paper-based writing scores. The results of the paired samples t-test showed no statistically significant difference between high- and low-computer-familiar groups on computer-based writing. The researchers concluded that the two modes comparably measured the same construct.

  18. DFT Study On Effects of CO2 Contamination in Non-Aqueous Li-Air Batteries

    DEFF Research Database (Denmark)

    Mekonnen, Yedilfana Setarge; Mýrdal, Jón Steinar Garðarsson; Vegge, Tejs

    2013-01-01

    Density Functional Theory (DFT) studies on the effects of carbon dioxide (CO2) contamination at the cathode of rechargeable non-aqueous Li-O2 batteries, where the insulating material Lithium peroxide (Li2O2) is the main discharge product. The Li2O2 growth mechanism and overpotentials are investig...... and result in an increased battery capacity. However, CO2 contamination on the Li2O2 surface confirms an asymmetric increase in the overpotentials; particularly the charging overvoltage exhibits sustantial increase, which would reduce the efficiency of the Li-air battery.......Density Functional Theory (DFT) studies on the effects of carbon dioxide (CO2) contamination at the cathode of rechargeable non-aqueous Li-O2 batteries, where the insulating material Lithium peroxide (Li2O2) is the main discharge product. The Li2O2 growth mechanism and overpotentials...

  19. 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.

  20. 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.

  1. 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.

  2. Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials.

    Science.gov (United States)

    Verma, Prakash; Bartlett, Rodney J

    2014-05-14

    This paper's objective is to create a "consistent" mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization potentials (VIPs) of the molecule, as the latter condition attests to the viability of the exchange-correlation potential (VXC). None of the prominently used DFT approaches show these properties: the optimized effective potential VXC based ab initio dft does. A local, range-separated hybrid potential cam-QTP-00 is introduced as the basis for a "consistent" KS DFT approach. The computed VIPs as the negative of KS eigenvalue have a mean absolute error of 0.8 eV for an extensive set of molecule's electron ionizations, including the core. Barrier heights, equilibrium geometries, and magnetic properties obtained from the potential are in good agreement with experiment. A similar accuracy with less computational efforts can be achieved by using a non-variational global hybrid variant of the QTP-00 approach.

  3. 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).

  4. Theoretical analysis of the binding of iron(III) protoporphyrin IX to 4-methoxyacetophenone thiosemicarbazone via DFT-D3, MEP, QTAIM, NCI, ELF, and LOL studies.

    Science.gov (United States)

    Nkungli, Nyiang Kennet; Ghogomu, Julius Numbonui

    2017-07-01

    Thiosemicarbazones display diverse pharmacological properties, including antimalarial activities. Their pharmacological activities have been studied in depth, but little of this research has focused on their antimalarial mode of action. To elucidate this antimalarial mechanism, we investigated the nature of the interactions between iron(III) protoporphyrin IX (Fe(III)PPIX) and the thione-thiol tautomers of 4-methoxyacetophenone thiosemicarbazone (MAPTSC). Dispersion-corrected density functional theory (DFT-D3), the quantum theory of atoms in molecules (QTAIM), the noncovalent interaction (NCI) index, the electron localization function (ELF), the localized orbital locator (LOL), and thermodynamic calculations were employed in this work. Fe(III)PPIX-MAPTSC binding is expected to inhibit hemozoin formation, thereby preventing Fe(III)PPIX detoxification in plasmodia. Preliminary studies geared toward the identification of atomic binding sites in the thione-thiol tautomers of MAPTSC were carried out using molecular electrostatic potential (MEP) maps and conceptual DFT-based local reactivity indices. The thionic sulfur and the 2 N-azomethine nitrogen/thiol sulfur of, respectively, the thione and thiol tautomers of MAPTSC were identified as the most favorable nucleophilic sites for electrophilic attack. The negative values of the computed Fe(III)PPIX-MAPTSC binding energies, enthalpies, and Gibbs free energies are indicative of the existence and stability of Fe(III)PPIX-MAPTSC complexes. MAPTSC-Fe(III) coordinate bonds and strong hydrogen bonds (N-H···O) between the NH 2 group in MAPTSC and the C=O group in one propionate side chain of Fe(III)PPIX are crucial to Fe(III)PPIX-MAPTSC binding. QTAIM, NCI, ELF, and LOL analyses revealed a subtle interplay of weak noncovalent interactions dominated by dispersive-like van der Waals interactions between Fe(III)PPIX and MAPTSC that stabilize the Fe(III)PPIX-MAPTSC complexes.

  5. A projected preconditioned conjugate gradient algorithm for computing many extreme eigenpairs of a Hermitian matrix

    International Nuclear Information System (INIS)

    Vecharynski, Eugene; Yang, Chao; Pask, John E.

    2015-01-01

    We present an iterative algorithm for computing an invariant subspace associated with the algebraically smallest eigenvalues of a large sparse or structured Hermitian matrix A. We are interested in the case in which the dimension of the invariant subspace is large (e.g., over several hundreds or thousands) even though it may still be small relative to the dimension of A. These problems arise from, for example, density functional theory (DFT) based electronic structure calculations for complex materials. The key feature of our algorithm is that it performs fewer Rayleigh–Ritz calculations compared to existing algorithms such as the locally optimal block preconditioned conjugate gradient or the Davidson algorithm. It is a block algorithm, and hence can take advantage of efficient BLAS3 operations and be implemented with multiple levels of concurrency. We discuss a number of practical issues that must be addressed in order to implement the algorithm efficiently on a high performance computer

  6. 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.

  7. Computational and Experimental Insight Into Single-Molecule Piezoelectric Materials

    Science.gov (United States)

    Marvin, Christopher Wayne

    Piezoelectric materials allow for the harvesting of ambient waste energy from the environment. Producing lightweight, highly responsive materials is a challenge for this type of material, requiring polymer, foam, or bio-inspired materials. In this dissertation, I explore the origin of the piezoelectric effect in single molecules through density functional theory (DFT), analyze the piezoresponse of bio-inspired peptidic materials through the use of atomic and piezoresponse force microscopy (AFM and PFM), and develop a novel class of materials combining flexible polyurethane foams and non-piezoelectric, polar dopants. For the DFT calculations, functional group, regiochemical, and heteroatom derivatives of [6]helicene were examined for their influence on the piezoelectric response. An aza[6]helicene derivative was found to have a piezoelectric response (108 pm/V) comparable to ceramics such as lead zirconium titanate (200+ pm/V). These computed materials have the possibility to compete with current field-leading piezomaterials such as lead zirconium titanate (PZT), zinc oxide (ZnO), and polyvinylidene difluoride (PVDF) and its derivatives. The use of AFM/PFM allows for the demonstration of the piezoelectric effect of the selfassembled monolayer (SAM) peptidic systems. Through PFM, the influence that the helicity and sequence of the peptide has on the overall response of the molecule can be analyzed. Finally, development of a novel class of piezoelectrics, the foam-based materials, expands the current understanding of the qualities required for a piezoelectric material from ceramic and rigid materials to more flexible, organic materials. Through the exploration of these novel types of piezoelectric materials, new design rules and figures of merit have been developed.

  8. Soil Erosion Estimation Using Grid-based Computation

    Directory of Open Access Journals (Sweden)

    Josef Vlasák

    2005-06-01

    Full Text Available Soil erosion estimation is an important part of a land consolidation process. Universal soil loss equation (USLE was presented by Wischmeier and Smith. USLE computation uses several factors, namely R – rainfall factor, K – soil erodability, L – slope length factor, S – slope gradient factor, C – cropping management factor, and P – erosion control management factor. L and S factors are usually combined to one LS factor – Topographic factor. The single factors are determined from several sources, such as DTM (Digital Terrain Model, BPEJ – soil type map, aerial and satellite images, etc. A conventional approach to the USLE computation, which is widely used in the Czech Republic, is based on the selection of characteristic profiles for which all above-mentioned factors must be determined. The result (G – annual soil loss of such computation is then applied for a whole area (slope of interest. Another approach to the USLE computation uses grids as a main data-structure. A prerequisite for a grid-based USLE computation is that each of the above-mentioned factors exists as a separate grid layer. The crucial step in this computation is a selection of appropriate grid resolution (grid cell size. A large cell size can cause an undesirable precision degradation. Too small cell size can noticeably slow down the whole computation. Provided that the cell size is derived from the source’s precision, the appropriate cell size for the Czech Republic varies from 30m to 50m. In some cases, especially when new surveying was done, grid computations can be performed with higher accuracy, i.e. with a smaller grid cell size. In such case, we have proposed a new method using the two-step computation. The first step computation uses a bigger cell size and is designed to identify higher erosion spots. The second step then uses a smaller cell size but it make the computation only the area identified in the previous step. This decomposition allows a

  9. Structural changes in the water tetramer. A combined Monte Carlo and DFT study

    Czech Academy of Sciences Publication Activity Database

    Vítek, A.; Kalus, R.; Paidarová, Ivana

    2010-01-01

    Roč. 12, č. 41 (2010), s. 13657-13666 ISSN 1463-9076 R&D Projects: GA AV ČR IAA401870702 Institutional research plan: CEZ:AV0Z40400503 Keywords : Monte Carlo Study * DFT study * water tetramer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.454, year: 2010

  10. Big data mining analysis method based on cloud computing

    Science.gov (United States)

    Cai, Qing Qiu; Cui, Hong Gang; Tang, Hao

    2017-08-01

    Information explosion era, large data super-large, discrete and non-(semi) structured features have gone far beyond the traditional data management can carry the scope of the way. With the arrival of the cloud computing era, cloud computing provides a new technical way to analyze the massive data mining, which can effectively solve the problem that the traditional data mining method cannot adapt to massive data mining. This paper introduces the meaning and characteristics of cloud computing, analyzes the advantages of using cloud computing technology to realize data mining, designs the mining algorithm of association rules based on MapReduce parallel processing architecture, and carries out the experimental verification. The algorithm of parallel association rule mining based on cloud computing platform can greatly improve the execution speed of data mining.

  11. Science World Journal

    African Journals Online (AJOL)

    The journal also promotes the application of computers in modeling and Bioinformatics. ... An improved map based graphical android authentication system · EMAIL ... DFT computations of the lattice constant, stable atomic structure and the ...

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

    Science.gov (United States)

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

    2015-06-01

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

  14. Inner ear malformations in patients with sensorineural heating loss: detection with gradient-echo (3DFT-CISS) MRI

    Energy Technology Data Exchange (ETDEWEB)

    Casselman, J.W. [Dept. of Radiology, A.Z. St.-Jan Brugge, Bruges (Belgium); Kuhweide, R. [Dept. of Otorhinolaryngology, A.Z. St.-Jan Brugge, Bruges (Belgium); Ampe, W. [Dept. of Otorhinolaryngology, A.Z. St.-Jan Brugge, Bruges (Belgium); D`Hont, G.D. [Dept. of Otorhinolaryngology, A.Z. St.-Jan Brugge, Bruges (Belgium); Offeciers, E.F. [ENT Dept., Sint-Augustinus Medical Inst., Univ. of Antwerp (Belgium); Faes, W.K. [Dept. of Radiology, A.Z. St.-Jan Brugge, Bruges (Belgium); Pattyn, G. [Dept. of Radiology, A.Z. St.-Jan Brugge, Bruges (Belgium)

    1996-04-01

    The sensitivity of different MRI sequences in the detection of inner ear malformations in patients presenting with sensorineural hearing loss (SNHL) and/or vertigo was evaluated. We studied 650 patients presenting with SNHL and/or vertigo, clinically not suspected of having inner ear malformations. The sensitivity of T1-weigted, Gd-enhanced T1-weighted and (when available) T2-weighted spin-echo images, and three-dimensional Fourier transformation-constructive interference in steady state (3DFT-CISS) gradient-echo images, to unexpected malformations was assessed. Inner ear malformations were found in 15 (2.3%) of these patients. Enlargement of the endolymphatic duct and sac was the most frequent malformation, found in 11 patients. The 3DFT-CISS images showed all lesions; the other sequences were less sensitive and the pathology was missed, partially or only retrospectively seen in 11 of the 15 patients. Therefore, in addition to the routine unenhanced and Gd-enhanced T1-weighted and T2-weighted images, thin gradient-echo (3DFT-CISS) images are necessary to detect all clinically unexpected inner ear malformations in patients presenting with vertigo and/or SNHL. (orig.)

  15. Inner ear malformations in patients with sensorineural heating loss: detection with gradient-echo (3DFT-CISS) MRI

    International Nuclear Information System (INIS)

    Casselman, J.W.; Kuhweide, R.; Ampe, W.; D'Hont, G.D.; Offeciers, E.F.; Faes, W.K.; Pattyn, G.

    1996-01-01

    The sensitivity of different MRI sequences in the detection of inner ear malformations in patients presenting with sensorineural hearing loss (SNHL) and/or vertigo was evaluated. We studied 650 patients presenting with SNHL and/or vertigo, clinically not suspected of having inner ear malformations. The sensitivity of T1-weigted, Gd-enhanced T1-weighted and (when available) T2-weighted spin-echo images, and three-dimensional Fourier transformation-constructive interference in steady state (3DFT-CISS) gradient-echo images, to unexpected malformations was assessed. Inner ear malformations were found in 15 (2.3%) of these patients. Enlargement of the endolymphatic duct and sac was the most frequent malformation, found in 11 patients. The 3DFT-CISS images showed all lesions; the other sequences were less sensitive and the pathology was missed, partially or only retrospectively seen in 11 of the 15 patients. Therefore, in addition to the routine unenhanced and Gd-enhanced T1-weighted and T2-weighted images, thin gradient-echo (3DFT-CISS) images are necessary to detect all clinically unexpected inner ear malformations in patients presenting with vertigo and/or SNHL. (orig.)

  16. SERS and DFT study of copper surfaces coated with corrosion inhibitor

    Directory of Open Access Journals (Sweden)

    Maurizio Muniz-Miranda

    2014-12-01

    Full Text Available Azole derivatives are common inhibitors of copper corrosion due to the chemical adsorption occurring on the metal surface that gives rise to a protective film. In particular, 1,2,4-triazole performs comparable to benzotriazole, which is much more widely used, but is by no means an environmentally friendly agent. In this study, we have analyzed the adsorption of 1,2,4-triazole on copper by taking advantage of the surface-enhanced Raman scattering (SERS effect, which highlights the vibrational features of organic ligand monolayers adhering to rough surfaces of some metals such as gold, silver and copper. To ensure the necessary SERS activation, a roughening procedure was implemented on the copper substrates, resulting in nanoscale surface structures, as evidenced by microscopic investigation. To obtain sufficient information on the molecule–metal interaction and the formation of an anticorrosive thin film, the SERS spectra were interpreted with the aid of theoretical calculations based on the density functional theory (DFT approach.

  17. Polycyclic Aromatic Hydrocarbons Adsorption onto Graphene: A DFT and AIMD Study

    Directory of Open Access Journals (Sweden)

    Bing Li

    2018-05-01

    Full Text Available Density functional theory (DFT calculations and ab-initio molecular dynamics (AIMD simulations were performed to understand graphene and its interaction with polycyclic aromatic hydrocarbons (PAHs molecules. The adsorption energy was predicted to increase with the number of aromatic rings in the adsorbates, and linearly correlate with the hydrophobicity of PAHs. Additionally, the analysis of the electronic properties showed that PAHs behave as mild n-dopants and introduce electrons into graphene; but do not remarkably modify the band gap of graphene, indicating that the interaction between PAHs and graphene is physisorption. We have also discovered highly sensitive strain dependence on the adsorption strength of PAHs onto graphene surface. The AIMD simulation indicated that a sensitive and fast adsorption process of PAHs can be achieved by choosing graphene as the adsorbent. These findings are anticipated to shed light on the future development of graphene-based materials with potential applications in the capture and removal of persistent aromatic pollutants.

  18. Impedance computations and beam-based measurements: A problem of discrepancy

    Science.gov (United States)

    Smaluk, Victor

    2018-04-01

    High intensity of particle beams is crucial for high-performance operation of modern electron-positron storage rings, both colliders and light sources. The beam intensity is limited by the interaction of the beam with self-induced electromagnetic fields (wake fields) proportional to the vacuum chamber impedance. For a new accelerator project, the total broadband impedance is computed by element-wise wake-field simulations using computer codes. For a machine in operation, the impedance can be measured experimentally using beam-based techniques. In this article, a comparative analysis of impedance computations and beam-based measurements is presented for 15 electron-positron storage rings. The measured data and the predictions based on the computed impedance budgets show a significant discrepancy. Three possible reasons for the discrepancy are discussed: interference of the wake fields excited by a beam in adjacent components of the vacuum chamber, effect of computation mesh size, and effect of insufficient bandwidth of the computed impedance.

  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. A combined experimental and DFT study of a novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine

    Science.gov (United States)

    Vijaya, P.; Sankaran, K. R.

    2015-03-01

    A novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine (UA) was prepared and characterized by IR, 1H and 13C NMR spectral studies. A 2D - potential energy scan (PES) of p-isobutylacetophenone (IBAP) was the portal to the conformational analysis of UA by density functional theory (DFT) methods using 6-31G(d,p) basis set by Gaussian 03 program. The theoretical IR frequencies were found to be in good agreement with the experimental values. The IR frequencies of UA were analyzed by means of Potential energy Distribution (PED %) calculation using Vibrational Energy Distribution Analysis (VEDA 4) program. The experimental NMR chemical shift values of UA were compared with the theoretical values obtained by DFT method. Nonlinear optical behavior of the unsymmetrical azine is also examined by the theoretically predicted values of dipole moment (μ), polarizability (α0) and first hyperpolarizability (βtot). Stability of the UA molecule has been analyzed using NBO analysis. The electrochemistry of UA studied experimentally by cyclic voltammetry is complemented by the computational analysis of the anionic form of the molecule UA. The determination of various global and local reactivity descriptors in the context of chemical reactivity is also performed and the electrophilicity at the vital atomic sites in UA is revealed. Bader's Atoms in molecules (AIM) theory of UA indicated the presence of intramolecular hydrogen bonding in the molecule. The molecular electrostatic potential (MEP) and HOMO-LUMO orbital analysis are also performed for the molecule UA.

  1. How Parallel Are Excited State Potential Energy Surfaces from Time-Independent and Time-Dependent DFT? A BODIPY Dye Case Study.

    Science.gov (United States)

    Komoto, Keenan T; Kowalczyk, Tim

    2016-10-06

    To support the development and characterization of chromophores with targeted photophysical properties, excited-state electronic structure calculations should rapidly and accurately predict how derivatization of a chromophore will affect its excitation and emission energies. This paper examines whether a time-independent excited-state density functional theory (DFT) approach meets this need through a case study of BODIPY chromophore photophysics. A restricted open-shell Kohn-Sham (ROKS) treatment of the S 1 excited state of BODIPY dyes is contrasted with linear-response time-dependent density functional theory (TDDFT). Vertical excitation energies predicted by the two approaches are remarkably different due to overestimation by TDDFT and underestimation by ROKS relative to experiment. Overall, ROKS with a standard hybrid functional provides the more accurate description of the S 1 excited state of BODIPY dyes, but excitation energies computed by the two methods are strongly correlated. The two approaches also make similar predictions of shifts in the excitation energy upon functionalization of the chromophore. TDDFT and ROKS models of the S 1 potential energy surface are then examined in detail for a representative BODIPY dye through molecular dynamics sampling on both model surfaces. We identify the most significant differences in the sampled surfaces and analyze these differences along selected normal modes. Differences between ROKS and TDDFT descriptions of the S 1 potential energy surface for this BODIPY derivative highlight the continuing need for validation of widely used approximations in excited state DFT through experimental benchmarking and comparison to ab initio reference data.

  2. Essential Means for Urban Computing: Specification of Web-Based Computing Platforms for Urban Planning, a Hitchhiker’s Guide

    Directory of Open Access Journals (Sweden)

    Pirouz Nourian

    2018-03-01

    Full Text Available This article provides an overview of the specifications of web-based computing platforms for urban data analytics and computational urban planning practice. There are currently a variety of tools and platforms that can be used in urban computing practices, including scientific computing languages, interactive web languages, data sharing platforms and still many desktop computing environments, e.g., GIS software applications. We have reviewed a list of technologies considering their potential and applicability in urban planning and urban data analytics. This review is not only based on the technical factors such as capabilities of the programming languages but also the ease of developing and sharing complex data processing workflows. The arena of web-based computing platforms is currently under rapid development and is too volatile to be predictable; therefore, in this article we focus on the specification of the requirements and potentials from an urban planning point of view rather than speculating about the fate of computing platforms or programming languages. The article presents a list of promising computing technologies, a technical specification of the essential data models and operators for geo-spatial data processing, and mathematical models for an ideal urban computing platform.

  3. DFT-Based Closed-form Covariance Matrix and Direct Waveforms Design for MIMO Radar to Achieve Desired Beampatterns

    KAUST Repository

    Bouchoucha, Taha; Ahmed, Sajid; Al-Naffouri, Tareq Y.; Alouini, Mohamed-Slim

    2017-01-01

    optimization problems. The computational complexity of these algorithms is very high, which makes them difficult to use in practice. In this paper, to achieve the desired beampattern, a low complexity discrete-Fourier-transform based closed-form covariance

  4. 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.

  5. 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...

  6. Computer based training: Technology and trends

    International Nuclear Information System (INIS)

    O'Neal, A.F.

    1986-01-01

    Computer Based Training (CBT) offers great potential for revolutionizing the training environment. Tremendous advances in computer cost performance, instructional design science, and authoring systems have combined to put CBT within the reach of all. The ability of today's CBT systems to implement powerful training strategies, simulate complex processes and systems, and individualize and control the training process make it certain that CBT will now, at long last, live up to its potential. This paper reviews the major technologies and trends involved and offers some suggestions for getting started in CBT

  7. Computational Fragment-Based Drug Design: Current Trends, Strategies, and Applications.

    Science.gov (United States)

    Bian, Yuemin; Xie, Xiang-Qun Sean

    2018-04-09

    Fragment-based drug design (FBDD) has become an effective methodology for drug development for decades. Successful applications of this strategy brought both opportunities and challenges to the field of Pharmaceutical Science. Recent progress in the computational fragment-based drug design provide an additional approach for future research in a time- and labor-efficient manner. Combining multiple in silico methodologies, computational FBDD possesses flexibilities on fragment library selection, protein model generation, and fragments/compounds docking mode prediction. These characteristics provide computational FBDD superiority in designing novel and potential compounds for a certain target. The purpose of this review is to discuss the latest advances, ranging from commonly used strategies to novel concepts and technologies in computational fragment-based drug design. Particularly, in this review, specifications and advantages are compared between experimental and computational FBDD, and additionally, limitations and future prospective are discussed and emphasized.

  8. Ab initio and DFT study of hydrogen bond interactions between ascorbic acid and dimethylsulfoxide based on FT-IR and FT-Raman spectra

    Science.gov (United States)

    Niazazari, Naser; Zatikyan, Ashkhen L.; Markarian, Shiraz A.

    2013-06-01

    The hydrogen bonding of 1:1 complexes formed between L-ascorbic acid (LAA) and dimethylsulfoxide (DMSO) has been studied by means of ab initio and density functional theory (DFT) calculations. Solutions of L-ascorbic acid (AA) in dimethylsulfoxide (DMSO) have been studied by means of both FT-IR (4000-220 cm-1) and FT-Raman spectroscopy. Ab initio Hartree-Fock (HF) and DFT methods have been used to determine the structure and energies of stable conformers of various types of L-AA/DMSO complexes in gas phase and solution. The basis sets 6-31++G∗∗ and 6-311+G∗ were used to describe the structure, energy, charges and vibrational frequencies of interacting complexes in the gas phase. The optimized geometric parameters and interaction energies for various complexes at different theories have been estimated. Binding energies have been corrected for basis set superposition error (BSSE) and harmonic vibrational frequencies of the structures have been calculated to obtain the stable forms of the complexes. The self-consistent reaction field (SCRF) has been used to calculate the effect of DMSO as the solvent on the geometry, energy and charges of complexes. The solvent effect has been studied using the Onsager models. It is shown that the polarity of the solvent plays an important role on the structures and relative stabilities of different complexes. The results obtained show that there is a satisfactory correlation between experimental and theoretical predictions.

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

    Science.gov (United States)

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

    2018-07-01

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

  10. The Activity-Based Computing Project - A Software Architecture for Pervasive Computing Final Report

    DEFF Research Database (Denmark)

    Bardram, Jakob Eyvind

    . Special attention should be drawn to publication [25], which gives an overview of the ABC project to the IEEE Pervasive Computing community; the ACM CHI 2006 [19] paper that documents the implementation of the ABC technology; and the ACM ToCHI paper [12], which is the main publication of the project......, documenting all of the project’s four objectives. All of these publication venues are top-tier journals and conferences within computer science. From a business perspective, the project had the objective of incorporating relevant parts of the ABC technology into the products of Medical Insight, which has been...... done. Moreover, partly based on the research done in the ABC project, the company Cetrea A/S has been founded, which incorporate ABC concepts and technologies in its products. The concepts of activity-based computing have also been researched in cooperation with IBM Research, and the ABC project has...

  11. 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

  12. DFT modeling of the electronic and magnetic structures and chemical bonding properties of intermetallic hydrides

    International Nuclear Information System (INIS)

    Al Alam, A.F.

    2009-06-01

    This thesis presents an ab initio study of several classes of intermetallics and their hydrides. These compounds are interesting from both a fundamental and an applied points of view. To achieve this aim two complementary methods, constructed within the DFT, were chosen: (i) pseudo potential based VASP for geometry optimization, structural investigations and electron localization mapping (ELF), and (ii) all-electrons ASW method for a detailed description of the electronic structure, chemical bonding properties following different schemes as well as quantities depending on core electrons such as the hyperfine field. A special interest is given with respect to the interplay between magneto-volume and chemical interactions (metal-H) effects within the following hydrided systems: binary Laves (e.g. ScFe 2 ) and Haucke (e.g. LaNi 5 ) phases on one hand, and ternary cerium based (e.g. CeRhSn) and uranium based (e.g. U 2 Ni 2 Sn) alloys on the other hand. (author)

  13. 3D-FT MRI of the facial nerve

    Energy Technology Data Exchange (ETDEWEB)

    Girard, N. (Neuroradiology, Hopital Nord, 13 Marseille (France)); Raybaud, C. (Neuroradiology, Hopital Nord, 13 Marseille (France)); Poncet, M. (Neuroradiology, Hopital Nord, 13 Marseille (France))

    1994-08-01

    Contrast-enhanced 3D-FT MRI of the intrapetrous facial nerve was obtained in 38 patients with facial nerve disease, using a 1.0 T magnet and fast gradient-echo acquisition sequences. Contiguous millimetric sections were obtained, which could be reformatted in any desired plane. Acutely ill patients, were examined within the first 2 months, included: 24 with Bell's palsy and 6 with other acute disorders (Herpes zoster, trauma, neuroma, meningeal metastasis, middle ear granuloma). Six patients investigated more than a year after the onset of symptoms included 3 with congenital cholesteatoma, 2 with neuromas and one with a chronic Bell's palsy. The lesion was found incidentally in two cases (a suspected neurofibroma and a presumed drop metastasis from an astrocytoma). Patients with tumours had nodular, focally-enhancing lesions, except for the leptomeningeal metastasis in which the enhancement was linear. Linear, diffuse contrast enhancement of the facial nerve was found in trauma, and in the patient with a middle ear granuloma. Of the 24 patients with an acute Bell's palsy 15 exhibited linear contrast enhancement of the facial nerve. Three of these were lost to follow-up, but correlation of clinical outcome and contrast enhancement showed that only 4 of the 11 patients who made a complete recovery and all 10 patients with incomplete recovery demonstrated enhancement. Possible explanations for these findings are suggested by pathological data from the literature. 3D-FT imaging of the facial nerve thus yields direct information about the of the nerve condition and defines the morphological abnormalities. It can also demonstrate contrast enhancement which seems to have some prognostic value in acute idiopathic Bell's palsy. (orig.)

  14. Development of Computer-Based Resources for Textile Education.

    Science.gov (United States)

    Hopkins, Teresa; Thomas, Andrew; Bailey, Mike

    1998-01-01

    Describes the production of computer-based resources for students of textiles and engineering in the United Kingdom. Highlights include funding by the Teaching and Learning Technology Programme (TLTP), courseware author/subject expert interaction, usage test and evaluation, authoring software, graphics, computer-aided design simulation, self-test…

  15. Enhancing school-based asthma education efforts using computer-based education for children.

    Science.gov (United States)

    Nabors, Laura A; Kockritz, Jennifer L; Ludke, Robert L; Bernstein, Jonathan A

    2012-03-01

    Schools are an important site for delivery of asthma education programs. Computer-based educational programs are a critical component of asthma education programs and may be a particularly important education method in busy school environments. The objective of this brief report is to review and critique computer-based education efforts in schools. The results of our literature review indicated that school-based computer education efforts are related to improved knowledge about asthma and its management. In some studies, improvements in clinical outcomes also occur. Data collection programs need to be built into games that improve knowledge. Many projects do not appear to last for periods greater than 1 year and little information is available about cultural relevance of these programs. Educational games and other programs are effective methods of delivering knowledge about asthma management and control. Research about the long-term effects of this increased knowledge, in regard to behavior change, is needed. Additionally, developing sustainable projects, which are culturally relevant, is a goal for future research.

  16. A chaotic modified-DFT encryption scheme for physical layer security and PAPR reduction in OFDM-PON

    Science.gov (United States)

    Fu, Xiaosong; Bi, Meihua; Zhou, Xuefang; Yang, Guowei; Li, Qiliang; Zhou, Zhao; Yang, Xuelin

    2018-05-01

    This letter proposes a modified discrete Fourier transform (DFT) encryption scheme with multi-dimensional chaos for the physical layer security and peak-to-average power ratio (PAPR) reduction in orthogonal frequency division multiplexing passive optical network (OFDM-PON) system. This multiple-fold encryption algorithm is mainly composed by using the column vectors permutation and the random phase encryption in the standard DFT matrix, which can create ∼10551 key space. The transmission of ∼10 Gb/s encrypted OFDM signal is verified over 20-km standard single mode fiber (SMF). Moreover, experimental results show that, the proposed scheme can achieve ∼2.6-dB PAPR reduction and ∼1-dB improvement of receiver sensitivity if compared with the common OFDM-PON.

  17. Computer Based Test Untuk Seleksi Masuk Politeknik Negeri Bengkalis

    Directory of Open Access Journals (Sweden)

    Agus Tedyyana

    2017-11-01

    Full Text Available AbstrakPenyeleksian calon mahasiswa baru dapat dilakukan dengan aplikasi Computer Based Test (CBT. Metode yang digunakan meliputi teknik pengumpulan data, analisis sistem, model perancangan, implementasi dan pengujian. Penelitian ini menghasilkan aplikasi CBT dimana soal yang dimunculkan dari bank soal melalui proses pengacakan dengan tidak akan memunculkan soal yang sama dengan menggunakan metoda Fisher-Yates Shuffle. Dalam proses pengamanan informasi soal saat terhubung ke jaringan maka diperlukan teknik untuk penyandian pesan agar soal tersebut sebeum dimunculkan melewati proses enkripsi dan deskripsi data terlebih dahulu maka digunakan algoritma kriptografi  RSA. Metode perancangan perangkat lunak menggunakan model waterfall, perancangan database menggunakan entity relationship diagram, perancangan antarmuka menggunakan hypertext markup language (HTML Cascading Style Sheet (CSS dan jQuery serta diimplementasikan berbasis web dengan menggunakan bahasa pemrograman PHP dan database MySQL, Arsitektur jaringan yang digunakan aplikasi Computer Based Test adalah model jaringan client-server dengan jaringan Local Area Network (LAN. Kata kunci: Computer Based Test, Fisher-Yates Shuffle, Criptography, Local Area Network AbstractSelection of new student candidates can be done with Computer Based Test (CBT application. The methods used include data collection techniques, system analysis, design model, implementation and testing. This study produces a CBT application where the questions raised from the question bank through randomization process will not bring up the same problem using the Fisher-Yates Shuffle method. In the process of securing information about the problem when connected to the network it is necessary techniques for encoding the message so that the problem before appear through the process of encryption and description of data first then used RSA cryptography algorithm. Software design method using waterfall model, database design

  18. Crystal structures and electronic properties of BaC2 isomers by theoretical study based on DFT

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Band structures and electronic properties of two BaC2 isomers were calculated by using density func-tional theory(DFT) properly.The ionic bond features are all typical between cation(Ba) and anion clusters(C2) in both structures of the isomers.However,a much stronger covalent bond exists in anion clusters which can be seen by inspecting the electron distribution contour that has a dull bell like shape between two carbon atoms.The shortest distance between Ba2+ and C22? and the bond length in anion clusters are different in these isomers of BaC2,which are 0.2945 nm and 0.1185 nm for the structure with the I4/mmm space group and 0.2744 and 0.1136 nm with the C2/c type,respectively.Band structures were clarified by combining the DOS to indicate the ionic bonding features more clearly.Population analysis provided further evidence on these ideas.Thermodynamical calculation results reveal that the transition temperature of these two polymorphs of BaC2 locates near 132 K,which is consistent with the recent experimental results.

  19. Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

    Energy Technology Data Exchange (ETDEWEB)

    Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

    2010-07-01

    Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

  20. 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.