Modified Becke’05 method of nondynamic correlation in density functional theory with self-consistent implementation

Proynov, Emil; Liu, Fenglai; Kong, Jing

doi:10.1016/j.cplett.2011.12.069

Cited by 13 publications

(11 citation statements)

References 22 publications

(15 reference statements)

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“…The present results confirm the previous findings 15,17,22,23,56 that the subtle structure of the NO dimer cannot be even remotely described properly without including explicitly ND correlation corrections in the method. Methods with full exact exchange and only a few fitting parameters, such as the functionals MCY2 and SCF-RI-B05 show some very good promise in describing the energetics of the NO dimer, while its geometry characteristics still remain elusive.…”

Section: The Strongly Correlated No Dimer Testsupporting

confidence: 91%

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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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Section: The Strongly Correlated No Dimer Testsupporting

confidence: 91%

“…(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%

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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“…B05, MCY2, and PSTS have been assessed by Liu et al, 133 using an efficient RI (resolution of the identity) implementation of Proynov et al [134][135][136] for self-consistent computations. They find that B05, MCY2, and PSTS do not perform quite as well as heavily parametrized meta-GGAs or LRC GGAs on standard thermochemical tests.…”

Section: Nonlocalitymentioning

confidence: 99%

“…Direct computation of the Slater potential on all grid points is costly, and differentiating B05 (or B13) with respect to orbital expansion coefficients for the purpose of self-consistent computations is daunting. Yet both of these tasks have been accomplished for B05 [134][135][136]205 and are therefore in hand for B13. Self-consistent B05/B13 computations are a few times lengthier than, e.g., B3LYP, but are not intractable thanks to RI (resolution of the identity) bases.…”

Section: Into the Futurementioning

confidence: 99%

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Perspective: Fifty years of density-functional theory in chemical physics

Becke

2014

The Journal of Chemical Physics

1,251

951

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Since its formal inception in 1964-1965, Kohn-Sham density-functional theory (KS-DFT) has become the most popular electronic structure method in computational physics and chemistry. Its popularity stems from its beautifully simple conceptual framework and computational elegance. The rise of KS-DFT in chemical physics began in earnest in the mid 1980s, when crucial developments in its exchange-correlation term gave the theory predictive power competitive with welldeveloped wave-function methods. Today KS-DFT finds itself under increasing pressure to deliver higher and higher accuracy and to adapt to ever more challenging problems. If we are not mindful, however, these pressures may submerge the theory in the wave-function sea. KS-DFT might be lost. I am hopeful the Kohn-Sham philosophical, theoretical, and computational framework can be preserved. This Perspective outlines the history, basic concepts, and present status of KS-DFT in chemical physics, and offers suggestions for its future development. © 2014 AIP Publishing LLC.

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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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Modified Becke’05 method of nondynamic correlation in density functional theory with self-consistent implementation

Cited by 13 publications

References 22 publications

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

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

Perspective: Fifty years of density-functional theory in chemical physics

Quantum Chemical Methods for Modeling Covalent Modification of Biological Thiols

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