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Basis Set (basis + set)
Kinds of Basis Set Terms modified by Basis Set Selected AbstractsOrbital-orthogonality constraints and basis-set optimizationJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2006Fabio E. Penotti Abstract A new procedure is presented for introducing arbitrary orbital-orthogonality constraints in the variational optimization of otherwise nonorthogonal multiconfiguration electronic wave functions. It is based on suitable analytical changes to the expressions for the first and second derivatives of the electronic energy with respect to the independent variational parameters, and can be applied in the presence of symmetry constraints. It is tested using a second-derivative optimization procedure, the Optimized Basis Set,Generalized Multiconfiguration Spin-Coupled (OBS-GMCSC) approach, that can treat basis-function exponential parameters as variational parameters, to be optimized simultaneously with configuration, spin-coupling, and orbital coefficients. This enables rigorous optimization of basis-set exponential parameters even for fully orthogonal multiconfiguration wave functions. Test calculations are carried out, with optimized even-tempered basis sets, on Li2 and on the CH radical. For the latter, special attention is paid to the electronic spin density at the nuclei. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 762,772, 2006 [source] Gaussian Basis Sets for Some Polyatomic Two-Heavy-Atom HydridesCHEMINFORM, Issue 50 2005Jose M. Pires Abstract For Abstract see ChemInform Abstract in Full Text. [source] Complete basis set extrapolations of dispersion, exchange, and coupled-clusters contributions to the interaction energy: a helium dimer study,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2008gorzata Jeziorska Abstract Effectiveness of various extrapolation schemes in predicting complete basis set (CBS) values of interaction energies has been investigated for the helium dimer as a function of interatomic separation R. The investigations were performed separately for the leading dispersion and exchange contributions to the interaction energy and for the interaction energy computed using the coupled cluster method with single and double excitations (CCSD). For all these contributions, practically exact reference values were obtained from Gaussian-type geminal calculations. Sequences of orbital basis sets augmented with diffuse and bond functions or augmented with two sets of diffuse functions have been employed, with the cardinal numbers up to X = 7. The functional form EX = ECBS + A(X , k),, was applied for the extrapolations, where EX is the contribution to the interaction energy computed with a basis set of cardinal number X. The main conclusion of this work is that CBS extrapolations of an appropriate functional form generally improve the accuracy of the interaction energies at a very small additional computational cost (of the order of 10%) and should be recommended in calculations of interatomic and intermolecular potentials. The effectiveness of the extrapolations significantly depends, however, on the interatomic separation R and on the composition of the basis set. Basis sets with midbond functions, well known to provide at a given size much more accurate nonextrapolated results than bases lacking such functions, have been found to perform best also in extrapolations. The X,1 extrapolations of dispersion energies computed with midbond function turned out to be very efficient (except at large R), reducing the errors by an order of magnitude for small X and a factor of two for large X (where the errors of nonextrapolated results are already very small). If midbond functions are not used, the X,3 formula is most appropriate for the dispersion energies. For the exchange component of the interaction energy, the best results are obtained,in both types of basis sets,with the X,4 extrapolation, which leads (in both cases) to almost an order of magnitude reduction of the error. The X,3 and (X , 1),3 extrapolations work also well, but give smaller improvements. The correlation component of the CCSD interaction energy extrapolates best with , between 2 and 3 for bases with midbond functions and between 3 and 4 for bases without such functions. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Relativistic correlating basis sets for actinide atoms from 90Th to 103LrJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2007Takeshi Noro Abstract For 14 actinide atoms from 90Th to 103Lr, contracted Gaussian-type function sets are developed for the description of correlations of the 5f, 6d, and 7s electrons. Basis sets for the 6d orbitals are also prepared, since the orbitals are important in molecular environments despite their vacancy in the ground state of some actinides. A segmented contraction scheme is employed for the compactness and efficiency. Contraction coefficients and exponents are so determined as to minimize the deviation from accurate natural orbitals of the lowest term arising from the 5fn,16d17s2 configuration. The spin-free relativistic effects are considered through the third-order Douglas-Kroll approximation. To test the present correlating sets, all-electron calculations are performed on the ground state of 90ThO molecule. The calculated spectroscopic constants are in excellent agreement with experimental values. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Calculated on 1H and 13C NMR chemical shifts of 2,4-difluorobenzaldehyde isonicotinoylhydrazone and 2,3-dichlorobenzaldehyde isonicotinoylhydrazone with GIAO, IGAIM, and CSGT modelsCONCEPTS IN MAGNETIC RESONANCE, Issue 5 2009N. Günay Abstract The 1H and 13C NMR chemical shifts of the 2,4-difluorobenzaldehyde isonicotinoylhydrazone (I) and 2,3-dichlorobenzaldehyde isonicotinoylhydrazone (II) were determined with the help of full spectral analysis. The geometry and electronic structure of the title compounds were investigated at both the ab initio Hartree-Fock and the B3LYP levels with 6-31+G(d,p) basis set. The NMR data were calculated by means of the GIAO, CSGT, and IGAIM methods. All quantum-chemical calculations, including those of NMR data, were performed by ab initio level HF and DFT methods. Excellent agreement between the theoretical and experimental results was found for the HF level 1H and 13C chemical shifts. The parameters of molecular geometry and 1H and 13C chemical shift values of the title compounds (I, II) in the ground state have been calculated and and compared with corresponding experimental result. © 2009 Wiley Periodicals, Inc. Concepts Magn Reson Part A 34A: 297,304, 2009. [source] J -Based Analysis and DFT,NMR Assignments of Natural Complex Molecules: Application to 3,,7-Dihydroxy-5,6-epoxycholestanesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2008Jesús Javier Poza Abstract In order to reproduce the stereochemical dispositions of the epoxy and hydroxy functionalities, four 3,,7-hydroxy-5,6-epoxycholestanes were easily prepared from cholesterol, and their NMR spectroscopic data were experimentally obtained from 1D and 2D NMR experiments. An exhaustive QM- J -based analysis was then performed to replicate the experimental H,H and C,H coupling constants as well as the 13C NMR chemical shifts. The B3LYP GIAO methodology with the 6-311-G(d,p) basis set was chosen and showed that the data obtained from rings A and B were sufficient to calculate the correct stereochemistry of the 5,6-epoxy and 7-hydroxy groups. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Body-wave traveltime and amplitude shifts from asymptotic travelling wave couplingGEOPHYSICAL JOURNAL INTERNATIONAL, Issue 2 2006F. Pollitz SUMMARY We explore the sensitivity of finite-frequency body-wave traveltimes and amplitudes to perturbations in 3-D seismic velocity structure relative to a spherically symmetric model. Using the approach of coupled travelling wave theory, we consider the effect of a structural perturbation on an isolated portion of the seismogram. By convolving the spectrum of the differential seismogram with the spectrum of a narrow window taper, and using a Taylor's series expansion for wavenumber as a function of frequency on a mode dispersion branch, we derive semi-analytic expressions for the sensitivity kernels. Far-field effects of wave interactions with the free surface or internal discontinuities are implicitly included, as are wave conversions upon scattering. The kernels may be computed rapidly for the purpose of structural inversions. We give examples of traveltime sensitivity kernels for regional wave propagation at 1 Hz. For the direct SV wave in a simple crustal velocity model, they are generally complicated because of interfering waves generated by interactions with the free surface and the Mohorovi,i, discontinuity. A large part of the interference effects may be eliminated by restricting the travelling wave basis set to those waves within a certain range of horizontal phase velocity. [source] Rearrangements in Model Peptide-Type Radicals via Intramolecular Hydrogen-Atom TransferHELVETICA CHIMICA ACTA, Issue 10 2006Damian Moran Abstract Intramolecular H-atom transfer in model peptide-type radicals was investigated with high-level quantum-chemistry calculations. Examination of 1,2-, 1,3-, 1,5-, and 1,6[C,,,N]-H shifts, 1,4- and 1,7[C,,,C]-H shifts, and 1,4[N,,,N]-H shifts (Scheme,1), was carried out with a number of theoretical methods. In the first place, the performance of UB3-LYP (with the 6-31G(d), 6-31G(2df,p), and 6-311+G(d,p) basis sets) and UMP2 (with the 6-31G(d) basis set) was assessed for the determination of radical geometries. We found that there is only a small basis-set dependence for the UB3-LYP structures, and geometries optimized with UB3-LYP/6-31G(d) are generally sufficient for use in conjunction with high-level composite methods in the determination of improved H-transfer thermochemistry. Methods assessed in this regard include the high-level composite methods, G3(MP2)-RAD, CBS-QB3, and G3//B3-LYP, as well as the density-functional methods B3-LYP, MPWB1K, and BMK in association with the 6-31+G(d,p) and 6-311++G(3df,3pd) basis sets. The high-level methods give results that are close to one another, while the recently developed functionals MPWB1K and BMK provide cost-effective alternatives. For the systems considered, the transformation of an N-centered radical to a C-centered radical is always exothermic (by 25,kJ,,,mol,1 or more), and this can lead to quite modest barrier heights of less than 60,kJ,,,mol,1 (specifically for 1,5[C,,,N]-H and 1,6[C,,,N]-H shifts). H-Migration barriers appear to decrease as the ring size in the transition structure (TS) increases, with a lowering of the barrier being found, for example when moving from a rearrangement proceeding via a four-membered-ring TS (e.g., the 1,3[C,,,N]-H shift, CH3C(O)NH.,,,.CH2C(O)NH2) to a rearrangement proceeding via a six-membered-ring TS (e.g., the 1,5[C,,,N]-H shift, .NHCH2C(O)NHCH3,,,NH2CH2C(O)NHCH2.). [source] Theoretical studies on thiabenzene and its fused derivatives: DFT and ab initio computationsHETEROATOM CHEMISTRY, Issue 5 2006M. Z. Kassaee The molecular structures of thiabenzene (1), 1-thianaphthalene (2), 2-thianaphthalene (3), and 9-thiaanthracene (4) are studied using HF and DFT methods with 6-31+G* basis set. The nonplanar boat conformers of 1,4, with 6,-electrons in their heterocyclic ring, appear more stable than the corresponding planar conformers with 8,-electrons in the ring. This study focuses on the stability, the ylide character, the inversion barrier energy of sulfur atoms, and the conformational flexibility of the ring in 1,4. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:376,381, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20214 [source] Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo-triplet splittingHETEROATOM CHEMISTRY, Issue 4 2006Khodayar Gholivand Some new phosphoramidates, 1,3, and the corresponding cyclophosphazanes, 4,6, with formula Cl2P(p -NHC6H4CH3) 1, Cl2P(O)(p -NHC6H4NO2) 2, (CH3)2NP(O)Cl(p -NHC6H4CH3)3, [ClP(p -NC6H4CH3)]24, [ClP(O)(p -NC6H4NO2)]25, and [(CH3)2NP(O)(p -NC6H4CH3)]26 were synthesized and characterized by 1H, 13C, 31P NMR, IR, mass spectroscopy, and elemental analysis. A pseudo-triplet signal was observed in the 1H NMR spectrum of molecule 6 for the N(CH3)2 protons. The A6A, 6X2 spin system was suggested for the pseudo-triplet pattern of 3JPNCH coupling in this molecule. Ab initio calculations were performed at the HF and B3LYP levels of theory with 6-311G** standard basis set on the geometry of compound 6. Also, the NMR chemical shift calculations were done to compare the computed results with the experimental ones. The calculated results are in good agreement with experimental data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:337,343, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20229 [source] An ab initio valence bond (VB) calculation of the , delocalization energy in borazine, B3N3H6,HETEROATOM CHEMISTRY, Issue 5 2005Daniel Benker Valence bond (VB) calculations using a double-zeta D95 basis set have been performed for borazine, B3N3H6 and for benzene, C6H6 in order to determine the relative weights of individual standard Lewis structures. In the delocalized resonance scheme of borazine, the structure (I) with no double bonds and three lone pairs of electrons at the three nitrogen atoms is the major contributor with a structural weight of 0.17, followed by six equivalent Lewis structures with one double bond and two lone pairs at two nitrogen atoms (II) with weights of 0.08 each. In the case of benzene, the two Kekulé structures (III) contribute with structural weights of 0.15 each, followed by 12 equivalent ionic structures (IV) with weights of 0.03 each, followed by the three equivalent Dewar-type structures (V) with structural weights of 0.02 each. The values of 54.1 and 45.8 kcal mol,1 for the delocalization energies of borazine and benzene were estimated. Therefore, B3N3H6 is calculated to have substantial aromatic character, similar to benzene, when we assume that the resonance energy can provide a criterion for aromaticity. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:311,315, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20095 [source] Comparative theoretical study of small Rhn nanoparticles (2 , n , 8) using DFT methodsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2010V. Bertin Abstract This work is aimed at identifying some key characteristics (energy, geometry, and spin) concerning Rhn particles (2 = n , 8) to perform further studies on adsorption and coadsorption sites of pollutants (CO and NO). The DFT methods of the Gaussian 03 program with the LANL2DZ basis set and the LANL2 potential are used. With the purpose to obtain a better nanoparticles definition, five different functionals were tested: B3LYP, O3LYP, BPW91, BP86, and HCTH; and the corresponding results are used to determine which of them best describes distances, spin, and gives acceptable highest vibration frequency and binding energy values, by comparing these results with values measured or calculated by many other authors. For the structure optimization process of the particles, the initial geometric shape was taken mainly from the literature, using the Rh,Rh distance: 2.67 Å, known for the bulk; and doing a complete optimization. We also considered flat nanoparticles structures, which most of them display three-dimensional structures after the optimization process. The few flat shapes are mainly higher in energy than those of three-dimensional structure. For some Rhn particles for different n values, the spin of the ground state present degeneration. In some cases, the optimization process changes the initial geometry, but in most cases, there are only minor changes in bonds and geometry. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Intramolecular hydrogen bond in 3-imino-propenylamine isomers: AIM and NBO studiesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2010H. Raissi Abstract The molecular structure and intramolecular hydrogen bond energy of 18 conformers of 3-imino-propenyl-amine were investigated at MP2 and B3LYP levels of theory using the standard 6-311++G** basis set. The atom in molecules or AIM theory of Bader, which is based on the topological properties of the electron density (,), was used additionally and the natural bond orbital (NBO) analysis was also carried out. Furthermore calculations for all possible conformations of 3-imino-propenyl-amin in water solution were also carried out at B3LYP/6-311++G** and MP2/6-311++G** levels of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the imine,amine conformers of this compound are more stable than the other conformers. B3LYP method predicts the IMA-1 as global minimum. This stability is mainly due to the formation of a strong NH···N intramolecular hydrogen bond, which is assisted by ,-electrons resonance, and this ,-electrons are established by NH2 functional group. Hydrogen bond energies for all conformers of 3-imino-propenyl-amine were obtained from the related rotamers methods. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Ab initio quantum-mechanical prediction of the IR and Raman spectra of Ca3Cr2Si3O12 Uvarovite garnetINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2010L. Valenzano Abstract The IR and Raman spectra of uvarovite (Ca3Cr2Si3O12) garnet were simulated with the periodic ab initio CRYSTAL code by adopting an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. The two sets of 17 F1u Transverse-Optical (TO) and Longitudinal-Optical (LO) frequencies are generated, together with their intensities. As regards the IR experimental spectrum, only five peaks are available, that are in excellent agreement with the calculated data (mean absolute difference smaller than 5.2 cm,1). The analysis of the TO-LO eigenvalue overlaps permits to establish a correspondence between LO and TO modes. The set of experimental Raman peaks is much reacher (23 out of 25) and the agreement with our calculations excellent ( smaller than 6 cm,1). Isotopic substitution is used to identify the zones of the spectrum where Cr and Ca contributions are relevant. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] My association with Frank Harris: An arc of forty-four yearsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2009Hendrik J. Monkhorst Abstract My collaborations with Frank Harris are reviewed. Besides reminiscing commentary on our long association, I explain the essentials of a recent proposal by Frank and me for a correlated basis set to implement the Molecular Coupled Cluster method I published in 1987. Its use will require the accurate evaluation of integrals over fully correlated Gaussian-type n body functions. This has been achieved for arbitrary n in a pair of publications. A third paper by Frank shows the way to include angular factors. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] The S and G transformations for computing three-center nuclear attraction integralsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2009Richard Mikael Slevinsky Abstract It is now well established that nonlinear transformations can be extremely useful in the case of oscillatory integrals. In previous work, we could show that the G transformation, which is not so well known among those interested in the numerical evaluation of highly oscillatory integrals, works very well for the extremely challenging integral called Twisted Tail. In this work, we demonstrate that these techniques also apply to three-center nuclear attraction integrals over exponential type functions. The accurate and rapid evaluation of these integrals is required in ab initio molecular structure calculations and density functional theory. Using a basis set of B functions and profiting from their relatively simple Fourier representation, these integrals are formulated as analytical expressions involving highly oscillatory spherical Bessel integral functions. In the present work, we implement two highly accurate algorithms for three-center nuclear attraction integrals. The first algorithm is based on the G transformation and the second is based on a combination of the S and G transformations. The application of these transformations is largely due to the properties of special functions that allow the computation of higher order derivatives of the integrands with exceptional simplicity. The numerical results illustrate the accuracy of these algorithms applied to three-center nuclear attraction integrals over exponential type functions with a miscellany of different parameters. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Chiral discrimination in hydrogen-bonded complexes of 2-methylol oxirane with hydrogen peroxideINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Guiqiu Zhang Abstract A systematic quantum chemical study reveals the effects of chirality on the intermolecular interactions between two chiral molecules bound by hydrogen bonds. The methods used are second-order Møller,Plesset perturbation theory (MP2) with the 6-311++g(d,p) basis set. Complexes via the OH···O hydrogen bond formed between the chiral 2-methylol oxirane (S) and chiral HOOH (P and M) molecules have been investigated, which lead to four diastereomeric complexes. The nomenclature of the complexes used in this article is enantiomeric configuration sign corresponding to English letters. Such as: sm, sp. The relative positions of the methylol group and the hydrogen peroxide are designated as syn (same side) and anti (opposite side). The largest chirodiastaltic energy was ,Echir = ,1.329 kcal mol,1 [9% of the counterpoise correct average binding energy De(corr)] between the sm-syn and sp-anti in favor of sm-syn. The largest diastereofacial energy was ,1.428 kcal mol,1 between sm-syn and sm-anti in favor of sm-syn. To take into account solvents effect, the polarizable continuum model (PCM) method has been used to evaluate the chirodiastaltic energies, and diastereofacial energies of the 2-methylol oxirane···HOOH complexes. The chiral 2,3-dimethylol oxirane (S, S) is C2 symmetry which offers two identical faces. Hence, the chirodiastaltic energy is identical to the diastereomeric energy, and is ,Echir = 0.563 kcal mol,1 or 5.3% of the De(corr) in favor of s,s-p. The optimized structures, interaction energies, and chirodiastaltic energies for various isomers were estimated. The harmonic frequencies, IR intensities, rotational constants, and dipole moments were also reported. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Comparative study on the nonadditivity of methyl group in lithium bonding and hydrogen bondingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Qingzhong Li Abstract Quantum chemical calculations at the second-order Moeller,Plesset (MP2) level with 6-311++G(d,p) basis set have been performed on the lithium-bonded and hydrogen-bonded systems. The interaction energy, binding distance, bond length, and stretch frequency in these systems have been analyzed to study the nonadditivity of methyl group in the lithium bonding and hydrogen bonding. In the complexes involving with NH3, the introduction of one methyl group into NH3 molecule results in an increase of the strength of lithium bonding and hydrogen bonding. The insertion of two methyl groups into NH3 molecule also leads to an increase of the hydrogen bonding strength but a decrease of the lithium bonding strength relative to that of the first methyl group. The addition of three methyl groups into NH3 molecule causes the strongest hydrogen bonding and the weakest lithium bonding. Although the presence of methyl group has a different influence on the lithium bonding and hydrogen bonding, a negative nonadditivity of methyl group is found in both interactions. The effect of methyl group on the lithium bonding and hydrogen bonding has also been investigated with the natural bond orbital and atoms in molecule analyses. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Structure and stability of high-spin Aun(n = 2,8) clustersINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2009Zhen-Yi Jiang Abstract The structures and relative stability of the maximum-spin n+1Aun and nAu (n = 2,8) clusters have been determined by density-functional theory. The structure optimizations and vibrational frequency analysis are performed with the gradient-corrections of Perdew along with his 1981 local correlation functional, combined with SBKJC effective core potential, augmented in the valence basis set by a set of f functions. We predicted the existence of a number of previously unknown isomers. The energetic and electronic properties of the small high-spin gold clusters are strongly dependent on sizes. The high-spin clusters tend to holding three-dimensional geometry rather than planar form preferred in low-spin situations. In whole high-spin Aun (n = 2,8) neutral and cationic species, 5Au4, 2Au, and 4Au are predicted to be of high stability, which can be explained by valence bond theory. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Complete basis set extrapolations of dispersion, exchange, and coupled-clusters contributions to the interaction energy: a helium dimer study,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2008gorzata Jeziorska Abstract Effectiveness of various extrapolation schemes in predicting complete basis set (CBS) values of interaction energies has been investigated for the helium dimer as a function of interatomic separation R. The investigations were performed separately for the leading dispersion and exchange contributions to the interaction energy and for the interaction energy computed using the coupled cluster method with single and double excitations (CCSD). For all these contributions, practically exact reference values were obtained from Gaussian-type geminal calculations. Sequences of orbital basis sets augmented with diffuse and bond functions or augmented with two sets of diffuse functions have been employed, with the cardinal numbers up to X = 7. The functional form EX = ECBS + A(X , k),, was applied for the extrapolations, where EX is the contribution to the interaction energy computed with a basis set of cardinal number X. The main conclusion of this work is that CBS extrapolations of an appropriate functional form generally improve the accuracy of the interaction energies at a very small additional computational cost (of the order of 10%) and should be recommended in calculations of interatomic and intermolecular potentials. The effectiveness of the extrapolations significantly depends, however, on the interatomic separation R and on the composition of the basis set. Basis sets with midbond functions, well known to provide at a given size much more accurate nonextrapolated results than bases lacking such functions, have been found to perform best also in extrapolations. The X,1 extrapolations of dispersion energies computed with midbond function turned out to be very efficient (except at large R), reducing the errors by an order of magnitude for small X and a factor of two for large X (where the errors of nonextrapolated results are already very small). If midbond functions are not used, the X,3 formula is most appropriate for the dispersion energies. For the exchange component of the interaction energy, the best results are obtained,in both types of basis sets,with the X,4 extrapolation, which leads (in both cases) to almost an order of magnitude reduction of the error. The X,3 and (X , 1),3 extrapolations work also well, but give smaller improvements. The correlation component of the CCSD interaction energy extrapolates best with , between 2 and 3 for bases with midbond functions and between 3 and 4 for bases without such functions. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Interaction of FeO+ cation with benzene, aniline, and 3-methylaniline: DFT study of oxygen insertion mechanismINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 11 2008Karolina Kwapien Abstract The reaction pathways and energetics for oxygen insertion into CH bond in benzene, aniline, and 3-methylaniline by FeO+ in the gas phase were investigated by means of the DFT methodology with the B3LYP exchange-correlation functional and 6-311G** basis set. The main aim of this work was to elucidate the influence of substituents in phenyl ring on stationary points along the energy profile on sextet and quartet surfaces for the reaction of FeO+ with substituted benzenes. The studies show that the amino and methyl groups change the energetics of oxygen insertion by lowering the energy profile along the reaction pathway. The substituents studied in this work facilitate the insertion of oxygen into the aromatic CH bond by stabilizing the intermediate sigma complex (,-complex), the amino group being by far more effective. On the other hand, both functional groups increase the activation energy of the rate-determining step in the gas phase, so that they have unfavorable influence on the kinetics. The comparison of the energy diagrams for the sextet and quartet spin states indicates the dominance of the low-spin reactivity in oxygen insertion into aromatic CH bond. Aniline and 3-methylaniline oxidation occurs via electrophilic addition while the conversion of benzene to phenol by FeO+ is mediated by a ,-complex with mixed radical and cationic character. Present results are also discussed in the context of oxyferryl group reactivity. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Mechanisms and kinetics for preparing carbohydrazide by reacting dimethyl carbonate with hydrazine: A theoretical studyINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 9 2008Jianguo Zhang Abstract The mechanism and kinetic modeling for preparing carbohydrazide from dimethyl carbonate and hydrazine has been declared. The geometries of all the stationary points (reactants, intermediates, transition states, and products) are optimized by using the B3LYP method with the cc-pVDZ basis set, and the harmonic vibrational frequencies as well as infrared intensities are predicted with the same method. The minimum-energy paths are obtained by using the intrinsic reaction coordinate (IRC) theory at the B3LYP/cc-pVDZ level of theory with the step length 0.02 (amu)1/2·bohr. The rate constants are evaluated by using the TST, TST/Eckart, and RRKM (T)/Eckart methods. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Mechanism for the gas-phase reaction between OH and 3-methylfuran: A theoretical studyINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2008Weichao Zhang Abstract The mechanism for the OH + 3-methylfuran reaction has been studied via ab initio calculations to investigate various reaction pathways on the doublet potential energy surface. Optimizations of the reactants, products, intermediates, and transition structures are conducted using the MP2 level of theory with the 6-311G(d,p) basis set. The single-point electronic energy of each optimized geometry is refined with G3MP2 and G3MP2B3 calculations. The theoretical study suggests that the OH + 3-methylfuran reaction is dominated by the formation of HC(O)CHC(CH3)CHOH (P7) and CH(OH)CHC(CH3)C(O)H (P9), formed from two low-lying adducts, IM1 and IM2. The direct hydrogen abstraction pathways and the SN2 reaction may play a minor or negligible role in the overall reaction of OH with 3-methylfuran. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Grid-based density functional calculations of many-electron systemsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Amlan K. RoyArticle first published online: 10 DEC 200 Abstract Exploratory variational pseudopotential density functional calculations are performed for the electronic properties of many-electron systems in the 3D cartesian coordinate grid (CCG). The atom-centered localized gaussian basis set, electronic density, and the two-body potentials are set up in the 3D cubic box. The classical Hartree potential is calculated accurately and efficiently through a Fourier convolution technique. As a first step, simple local density functionals of homogeneous electron gas are used for the exchange-correlation potential, while Hay-Wadt-type effective core potentials are employed to eliminate the core electrons. No auxiliary basis set is invoked. Preliminary illustrative calculations on total energies, individual energy components, eigenvalues, potential energy curves, ionization energies, and atomization energies of a set of 12 molecules show excellent agreement with the corresponding reference values of atom-centered grid as well as the grid-free calculation. Results for three atoms are also given. Combination of CCG and the convolution procedure used for classical Coulomb potential can provide reasonably accurate and reliable results for many-electron systems. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Internal-rotation and inversion potential energy surfaces for methylamine and methylphosphineINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Hae-Won Kim Abstract Using the HF, MP2, and DFT methods with a 6-311G** basis set, we examine the internal-rotation and inversion of the amino and phosphino groups in methylamine and methylphosphine. The resulting energy surfaces are reported as a function of rotation and inversion descriptors. Both surfaces are characterized by several special points: three minimum energy states, three first-order internal-rotation transition states, six first-order inversion transition states, and six second-order inversion transition states. The MP2 method gave better agreement with experiment. For methylamine, the MP2 energy barrier for internal-rotation is 8.73 kJ/mol; for first-order inversion it is 22.80 kJ/mol and for second-order inversion it is 22.41 kJ/mol. For methylphosphine, the MP2 energy barriers are 7.53, 149.88, and 149.65 kJ/mol, respectively. The energy barriers include ZPE correction contributions. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Substituent effects on O,H and S,H bond dissociation enthalpies of disubstituted phenols and thiophenolsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2008Daniel J. V. A. dos Santos Abstract The O,H and S,H homolytic bond dissociation enthalpies of a set of disubstituted phenols and thiophenols (NH2, OH, CH3, Cl, CF3, and NO2) have been computed by a density functional theory procedure with the 6-311++G(d,p) basis set. A very good agreement between our results and available experimental ones is observed. The effect of substituents on structure, charges and BDEs are investigated and their correlation with Hammett parameters is studied. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Tayloring standard TDDFT approaches for computing UV/Vis transitions in thiocarbonyl chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2008Julien Preat Abstract We report the development of an accurate computational procedure for the calculation of the n , ,* (,max,1) and , , ,* (,max,2) transitions of a set of thiocarbonyl derivatives. To ensure converged results, all calculations are carried out using the 6-311+G(2df,p) basis set for time-dependent calculations, and the 6-311G(2df,p) for the ground-state geometrical optimization. Starting with two hybrids, PBE0 and B3LYP, the Hartree,Fock exchange percentage (,) used is optimized in order to reach excitation energies that fit experimental data. It turns out that BLYP(,) is the more adequate functional for calibration. For the n , ,* excitation, the optimal , value lies in the 0.10,0.20 interval, whereas for the , , ,* process setting , equal to 0.10 provides the most accurate results. The corresponding mean absolute errors (MAE) are limited to 17 nm for ,max,1, and to 10 nm for ,max,2, allowing a consistent and accurate prediction of both transitions. We also assess the merits of the ZINDO//AM1 scheme and it turns out that the semi-empirical method only provides a poor prediction of the ,max of thiocarbonyl derivatives, especially for the n , ,* transition. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Theoretical study of hydrogen-bonded complexes of benzene with hydrides of astrochemical interestINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2008M. Nait Achour Abstract Post Hartree,Fock and DFT calculations have been performed for studying the possibility for a benzene support to be linked to various hydrides through a quasi Bz···HA bond. Interaction energy of compounds, including CH bonds (CH4, CH3F, CH2O, CHN, CHNO), NH bonds (NH3, NH2F, NHC, NHCO, NH3O), and OH bonds (OH2, OHF, NCOH), were evaluated, taking basis set superposition error (BSSE) and zero point vibrational energy (ZPVE) corrections into account. Numerical convergence of results with respect to the ingredients included at different steps of theory (basis set, DFT functionals, correlation treatments, geometry optimization) was tested mainly on the example of the water adduct and, for comparison, the Bz···H3O+ system containing a cation instead of a neutral molecule. A rather large range of adsorption energies is obtained, from about 1 kcal/mol for methane to more than 6 kcal/mol for cyanic acid, according to the acidic character of the adsorbed species in each family of Bz···HA bonds. Some consequences for astrophysical problems involving PAHs in the interstellar medium are pointed out. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Comparative study of unscreened and screened molecular static linear polarizability in the Hartree,Fock, hybrid-density functional, and density functional modelsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2008Rajendra R. Zope Abstract The sum-over-states (SOS) polarizabilities are calculated within approximate mean-field electron theories such as the Hartree,Fock approximation and density functional models using the eigenvalues and orbitals obtained from the self-consistent solution of the single-particle equations. The SOS polarizabilities are then compared with those calculated using the finite-field (FF) method. Three widely used mean-field models are as follows: (1) the Hartree,Fock (HF) method, (2) the three parameter hybrid generalized gradient approximation (GGA) (B3LYP), and (3) the parameter-free generalized gradient approximation due to Perdew,Burke,Ernzerhof (PBE). The comparison is carried out for polarizabilities of 142 molecules calculated using the 6-311++G(d,p) basis set at the geometries optimized at the B3LYP/6-311G** level. The results show that the SOS method almost always overestimates the FF polarizabilities in the PBE and B3LYP models. This trend is reversed in the HF method. A few exceptions to these trends are found. The mean absolute errors (MAE) in the screened (FF) and unscreened (SOS) polarizability are 0.78, 1.87, and 3.44 Å3 for the HF, B3LYP, and PBE-GGA methods, respectively. Finally, a simple scheme is devised to obtain FF quality polarizability from the SOS polarizability. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Periodic models in quantum chemical simulations of F centers in crystalline metal oxidesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2007Yuri F. Zhukovskii Abstract We present a survey of recent first principles simulations of the neutral oxygen vacancies (F centers) existing as native or radiation-induced point defects in various crystalline metal oxides in different forms (bulk, bare substrate surface, and on the interface with metal adsorbates). We mainly consider periodic models in calculations of point defects using the metal oxide supercell or cyclic clusters. We compare different formalisms of first principles calculations, mostly the Density Functional Theory (DFT) as implemented in the framework of either localized basis set of atomic orbitals or delocalized basis sets of plane waves. We analyze in detail the structural and electronic properties of F centers in binary oxides of light metals (MgO and Al2O3), and ternary metal oxides (SrTiO3, BaTiO3, PbTiO3, KNbO3, and PbZrO3 perovskites). When available, we compare results of ab initio periodic defect calculations with experimental data, results of the first principles cluster calculations (both embedded and molecular) as well as with semi-empirical calculations. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] | ||||||||||||||||||||||||||||||||||