On the parameterization of the local correlation functional. What is Becke-3-LYP?

Hertwig, Roland H.; Koch, Wolfram

doi:10.1016/s0009-2614(97)00207-8

Cited by 947 publications

(540 citation statements)

References 18 publications

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“…For this purpose, an ample set of exchangecorrelation functionals has been used, namely LDA (VWN5) [70,71], BP86 [72,73], BLYP [72,74,75], B3LYP [72,76,77], CAMB3LYP [78], PBE [79], and PBE0 [80]. Moreover, it will allow for a detailed examination of internal consistency within the DFT contact densities owing to the approximate nature of the functionals.…”

Section: Electron Correlation Methodsmentioning

confidence: 99%

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Knecht

Fux

Meer³

et al. 2011

Theor Chem Acc

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The electrostatic contribution to the Mössbauer isomer shift of mercury for the series HgF n (n = 1, 2, 4) with respect to the neutral atom has been investigated in the framework of four-and two-component relativistic theory. Replacing the integration of the electron density over the nuclear volume by the contact density (that is, the electron density at the nucleus) leads to a 10% overestimation of the isomer shift. The systematic nature of this error suggests that it can be incorporated into a correction factor, thus justifying the use of the contact density for the calculation of the Mössbauer isomer shift. The performance of a large selection of density functionals for the calculation of contact densities has been assessed by comparing with finite-field four-component relativistic coupled-cluster with single and double and perturbative triple excitations [CCSD(T)] calculations. For the absolute contact density of the mercury atom, the Density Functional Theory (DFT) calculations are in error by about 0.5%, a result that must be judged against the observation that the change in contact density along the series HgF n (n = 1, 2, 4), relevant for the isomer shift, is on the order of 50 ppm with respect to absolute densities. Contrary to previous studies of the 57 Fe isomer shift (F Neese, Inorg Chim Acta 332:181, 2002), for mercury, DFT is not able to reproduce the trends in the isomer shift provided by reference data, in our case CCSD(T) calculations, notably the non-monotonous decrease in the contact density along the series HgF n (n = 1, 2, 4). Projection analysis shows the expected reduction of the 6s 1/2 population at the mercury center with an increasing number of ligands, but also brings into light an opposing effect, namely the increasing polarization of the 6s 1/2 orbital due to increasing effective charge of the mercury atom, which explains the nonmonotonous behavior of the contact density along the series. The same analysis shows increasing covalent contributions to bonding along the series with the effective charge of the mercury atom reaching a maximum of around ?2 for HgF 4 at the DFT level, far from the formal charge ?4 suggested by the oxidation state of this recently observed species. Whereas the geometries for the linear HgF 2 and square-planar HgF 4 molecules were taken from previous computational studies, we optimized the equilibrium distance of HgF at the four-component Fock-space CCSD/aug-cc-pVQZ level, giving spectroscopic constants r e = 2.007 Å and x e = 513.5 cm -1 .Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.Electronic supplementary material The online version of this article

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Section: Electron Correlation Methodsmentioning

confidence: 99%

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Knecht

Fux

Meer³

et al. 2011

Theor Chem Acc

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“…Most implementations of TDDFT utilize the adiabatic approximation where, in the limit of an electron density slowly varying in time, ground-state density functionals are used in the calculation of the time-dependent exchange-correlation potential. As a result, many applications of TDDFT in the literature employ either the popular global hybrid (GH) generalized-gradient approximation (GGA) B3LYP functional [7][8][9] or the GH version of the Perdew-Burke-Ernzerhoff (PBE0) exchangecorrelation functional. [10][11][12] With the maturity of DFT for the ground state, many new and more sophisticated density functionals have been [13][14][15][16][17][18][19][20][21][22][23][24][25] and continue to be developed.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking the performance of time-dependent density functional methods

Leang

Zahariev

Gordon

2012

The Journal of Chemical Physics

318

319

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The performance of 24 density functionals, including 14 meta-generalized gradient approximation (mGGA) functionals, is assessed for the calculation of vertical excitation energies against an experimental benchmark set comprising 14 small-to medium-sized compounds with 101 total excited states. The experimental benchmark set consists of singlet, triplet, valence, and Rydbergexcited states. The global-hybrid (GH) version of the Perdew-Burke-Ernzerhoff GGA density functional (PBE0) is found to offer the best overall performance with a mean absolute error (MAE) of 0. The performance of 24 density functionals, including 14 meta-generalized gradient approximation (mGGA) functionals, is assessed for the calculation of vertical excitation energies against an experimental benchmark set comprising 14 small-to medium-sized compounds with 101 total excited states. The experimental benchmark set consists of singlet, triplet, valence, and Rydberg excited states. The global-hybrid (GH) version of the Perdew-Burke-Ernzerhoff GGA density functional (PBE0) is found to offer the best overall performance with a mean absolute error (MAE) of 0.28 eV. The GH-mGGA Minnesota 2006 density functional with 54% Hartree-Fock exchange (M06-2X) gives a lower MAE of 0.26 eV, but this functional encounters some convergence problems in the ground state. The local density approximation functional consisting of the Slater exchange and Volk-Wilk-Nusair correlation functional (SVWN) outperformed all non-GH GGAs tested. The best pure density functional performance is obtained with the local version of the Minnesota 2006 mGGA density functional (M06-L) with an MAE of 0.41 eV.

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“…25 In this study, all structures were optimized using DFT with the B3LYP functional. 26, 27 Some additional calculations were performed with the B3PW91 functional 26 to compare with previous work. 15 As discussed in detail above, all DFT calculations at the restricted level were tested for orbital instabilities, and, if detected were re-optimized using unrestricted DFT.…”

Section: Methodsmentioning

confidence: 99%

Dalton Discussion 11: The renaissance of main group chemistry

Arnold¹

2008

Dalton Trans.

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Image reproduced with permission of Manfred ScheerPapers published in this issue include:The coordination chemistry of group 15 element ligand complexes-a developing area Manfred Scheer, Dalton Trans., 2008 DOI: 10.1039 Recent experimental and theoretical evidence has shown that distannynes, RSnSnR, can adopt either a singly bonded or a multiply bonded structure. Within calculations on small models, such as MeSnSnMe, apparently dramatic differences in conformational preference have been reported. We show that these differences arise due to the treatment of spin-polarization in density functional theory (DFT), and review stability analysis; a diagnostic for the need to include spin-polarization. The low-energy singly bonded structure can only be reached when spin-polarization is allowed. Additional DFT calculations on PhSnSnPh show that the singly bonded structure is the global minimum, leading to a flat torsional potential. The role of electronic effects is further probed by changing the donor-acceptor properties of R. Implications for the structural preference of experimentally synthesized species are discussed.

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On the parameterization of the local correlation functional. What is Becke-3-LYP?

Cited by 947 publications

References 18 publications

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Benchmarking the performance of time-dependent density functional methods

Dalton Discussion 11: The renaissance of main group chemistry

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