Improved self-consistent and resolution-of-identity approximated Becke'05 density functional model of nondynamic electron correlation

Proynov, Emil; Liu, Fenglai; Shao, Yihan; Kong, Jing

doi:10.1063/1.3676726

Cited by 37 publications

(57 citation statements)

References 38 publications

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“…(10) with sufficient accuracy. 13 In our implementation of PSTS we use a set of auxiliary Gaussian functions to expand the orbital basis function pairs, 15,22,23 …”

Section: A Pstsmentioning

confidence: 99%

“…Recently Becke's B05 method was implemented selfconsistently (the RI-B05 scheme 15 ) in the Q-Chem program. 19 The model was modified to make the selfconsistency feasible.…”

Section: Introductionmentioning

confidence: 99%

“…The advantage of this approach is that it is applicable to any type of orbital basis and is sufficiently accurate when the auxiliary basis set is properly constructed (see Ref. 15 for details). To verify the accuracy of the RI approach, we have calculated the total HF exchange energies of the first-and second-row atoms by summing the RI-approximated exact-exchange energy density over the atomic grids.…”

Section: A Pstsmentioning

confidence: 99%

“…The form of N eff Xσ (r) is quite complicated in the B05 model, but it is possible to represent it in a closed analytic form. 15,22 The last term of Eq. (27) is a second-order same-spin correction to the XC hole introduced to improve the performance for open-shell systems.…”

Section: B Mcy and B05 Functionalsmentioning

confidence: 99%

“…The rest of the cost is essentially the same as for the RI HF calculation. 15 We have recently applied this method for the calculation of the spin-resolved HF exchange energy density in a SCF implementation of the B05 method (the RI-B05 scheme 15,22 ). We have found that it yields accurate relative energies with a speed-up of hundreds of times compared to the exact implementation of Eq.…”

Section: A Pstsmentioning

confidence: 99%

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Comparison of the performance of exact-exchange-based density functional methods

Liu

Proynov²,

Yu³

et al. 2012

The Journal of Chemical Physics

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How to describe nondynamic electron correlation is still a major challenge to density functional theory (DFT). Recent models designed particularly for this problem, such as Becke'05 (B05) and Perdew-Staroverov-Tao-Scuseria (PSTS) functionals employ the exact-exchange density, the efficient calculation of which is technically quite challenging. We have recently implemented selfconsistently the B05 functional based on an efficient resolution-identity (RI) technique. In this study, we report a self-consistent RI implementation of the PSTS functional. In contrast to its original implementation, our version brings no limitation on the choice of the basis set. We have also implemented the Mori-Sanchez-Cohen-Yang-2 (MCY2) functional, another recent DFT method that includes full exact exchange. The performance of PSTS, B05, and MCY2 is validated on thermochemistry, reaction barriers, and dissociation energy curves, with an emphasis on nondynamic correlation effects in the discussion. All three methods perform rather well in general, B05 and MCY2 being on average somewhat better than PSTS. We include also results with other functionals that represent various aspects of the development in this field in recent years, including B3LYP, M06-HF, M06-2X, ωB97X, and TPSSh. The performance of the heavy-parameterized functionals M06-2X and ωB97X is on average better than that of B05, MCY2, and PSTS for standard thermodynamic properties and reactions, while the latter functionals do better in hydrogen abstraction reactions and dissociation processes. In particular, B05 is found to be the only functional that yields qualitatively correct dissociation curves for two-center symmetric radicals like He + 2 . Finally, we compare the performance of all these functionals on a strongly correlated exemplary case system, the NO dimer. Only PSTS, B05, and MCY2 describe the system qualitatively correctly. Overall, this new type of functionals show good promise of overcoming some of the difficulties DFT encounters for systems with strong nondynamic correlation.

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“…(10) with sufficient accuracy. 13 In our implementation of PSTS we use a set of auxiliary Gaussian functions to expand the orbital basis function pairs, 15,22,23 …”

Section: A Pstsmentioning

confidence: 99%

“…Recently Becke's B05 method was implemented selfconsistently (the RI-B05 scheme 15 ) in the Q-Chem program. 19 The model was modified to make the selfconsistency feasible.…”

Section: Introductionmentioning

confidence: 99%

Section: A Pstsmentioning

confidence: 99%

Section: B Mcy and B05 Functionalsmentioning

confidence: 99%

Section: A Pstsmentioning

confidence: 99%

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Comparison of the performance of exact-exchange-based density functional methods

Liu

Proynov²,

Yu³

et al. 2012

The Journal of Chemical Physics

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Quantum Chemical Methods for Modeling Covalent Modification of Biological Thiols

et al. 2019

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Targeted covalent inhibitor drugs require computational methods that go beyond simple molecular‐mechanical force fields in order to model the chemical reactions that occur when they bind to their targets. Here, several semiempirical and density‐functional theory (DFT) methods are assessed for their ability to describe the potential energy surface and reaction energies of the covalent modification of a thiol by an electrophile. Functionals such as PBE and B3LYP fail to predict a stable enolate intermediate. This is largely due to delocalization error, which spuriously stabilizes the prereaction complex, in which excess electron density is transferred from the thiolate to the electrophile. Functionals with a high‐exact exchange component, range‐separated DFT functionals, and variationally optimized exact exchange (i.e., the LC‐B05minV functional) correct this issue to various degrees. The large gradient behavior of the exchange enhancement factor is also found to significantly affect the results, leading to the improved performance of PBE0. While ωB97X‐D and M06‐2X were reasonably accurate, no method provided quantitative accuracy for all three electrophiles, making this a very strenuous test of functional performance. Additionally, one drawback of M06‐2X was that molecular dynamics (MD) simulations using this functional were only stable if a fine integration grid was used. The low‐cost semiempirical methods, PM3, AM1, and PM7, provide a qualitatively correct description of the reaction mechanism, although the energetics is not quantitatively reliable. As a proof of concept, the potential of mean force for the addition of methylthiolate to methylvinyl ketone was calculated using quantum mechanical/molecular mechanical MD in an explicit polarizable aqueous solvent. © 2019 Wiley Periodicals, Inc.

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TD-DFT benchmarks: A review

Laurent

Jacquemin

2013

Int. J. Quantum Chem

1,030

940

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International audienceTime-Dependent Density Functional Theory (TD-DFT) has become the most widely-used theoretical approach to simulate the optical properties of both organic and inorganic molecules. In this contribution, we review TD-DFT benchmarks that have been performed during the last decade. The aim is often to pinpoint the most accurate or adequate exchange-correlation functional(s). We present both the different strategies used to assess the functionals and the main results obtained in terms of accuracy. In particular, we discuss both vertical and adiabatic benchmarks and comparisons with both experimental and theoretical reference transition energies. More specific benchmarks (oscillator strengths, excited-state geometries, dipole moments, vibronic shapes, etc.) are summarized as well. (c) 2013 Wiley Periodicals, Inc

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Improved self-consistent and resolution-of-identity approximated Becke'05 density functional model of nondynamic electron correlation

Cited by 37 publications

References 38 publications

Comparison of the performance of exact-exchange-based density functional methods

Comparison of the performance of exact-exchange-based density functional methods

Quantum Chemical Methods for Modeling Covalent Modification of Biological Thiols

TD-DFT benchmarks: A review

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