The exchange-correlation potential in <i>ab initio</i> density functional theory

Bartlett, Rodney J.; Grabowski, Ireneusz; Hirata, So; Ivanov, Stanislav

doi:10.1063/1.1809605

Cited by 171 publications

(177 citation statements)

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“…Standard MP2 systematically underestimates the total energy on magnitude (up to more than 100 mhartree for Ar) which is partly due to the missing correlation contribution beyond second order and to the incompleteness of the basis sets used. On the opposite, OEP-GL2 sys- tematically gives too negative total energies, as already known [19,25]. For example, for CO the OEP-GL2 total energy is more than 150 mhartree too low.…”

Section: Resultsmentioning

confidence: 89%

“…At λ = 1, the 1DH approximation reduces to standard MP2 (with HF orbitals), while the OEP-1DH approximation reduces to OEP-GL2 (i.e., the same MP2 total energy expression but with fully self-consistently optimized OEP orbitals) [18,19]. Standard MP2 systematically underestimates the total energy on magnitude (up to more than 100 mhartree for Ar) which is partly due to the missing correlation contribution beyond second order and to the incompleteness of the basis sets used.…”

Section: Resultsmentioning

confidence: 99%

“…(2) (9) where v EXX [18][19][20]. We note that several alternative methods to OEP have been proposed [30][31][32][33][34][35][36], but we do not consider these alternative methods in this work.…”

Section: B Self-consistent Oep Double-hybrid Approximationsmentioning

confidence: 99%

“…The idea is to optimize the orbitals in the DH total energy expression by using a fully local potential corresponding to the complete exchange-correlation energy expression including the MP2 contribution. This can be considered as an extension of OEP schemes using arXiv:1607.05481v2 [physics.chem-ph] 23 Sep 2016 a second-order correlation energy expression [16][17][18][19][20].…”

Section: For a Review) In General Dh Approximationsmentioning

confidence: 99%

“…In practice, our OEP-1DH calculations employ a truncated singular-value decomposition (TSVD) method for the construction of the pseudoinverse of the linear-response function [used in Eqs. (18) and (19)] to ensure that stable and physically sound solutions are obtained in the OEP equations [Eqs. (10) and (11)].…”

Section: B Self-consistent Oep Double-hybrid Approximationsmentioning

confidence: 99%

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Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Śmiga

Franck

Mussard

et al. 2016

The Journal of Chemical Physics

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We introduce an orbital-optimized double-hybrid (DH) scheme using the optimized-effectivepotential (OEP) method. The orbitals are optimized using a local potential corresponding to the complete exchange-correlation energy expression including the second-order Møller-Plesset (MP2) correlation contribution. We have implemented a one-parameter version of this OEP-based selfconsistent DH scheme using the BLYP density-functional approximation and compared it to the corresponding non-self-consistent DH scheme for calculations on a few closed-shell atoms and molecules. While the OEP-based self-consistency does not provide any improvement for the calculations of ground-state total energies and ionization potentials, it does improve the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy. Moreover, the OEP-based self-consistent DH scheme provides reasonably accurate exchangecorrelation potentials and correlated densities.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: B Self-consistent Oep Double-hybrid Approximationsmentioning

confidence: 99%

Section: For a Review) In General Dh Approximationsmentioning

confidence: 99%

Section: B Self-consistent Oep Double-hybrid Approximationsmentioning

confidence: 99%

See 3 more Smart Citations

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Śmiga

Franck

Mussard

et al. 2016

The Journal of Chemical Physics

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Quantum Molecular Biological Methods Using Density Functional Theory

Jalkanen

Suhai

Bohr

2009

Digital Encyclopedia of Applied Physics

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The fields of quantum molecular biophysics and quantum molecular biology have recently experienced a revival. With the extension of density functional theoretical (DFT) methods to quantum chemistry, molecular biophysics and physical biology, the fundamental accuracy and physical rigor of the modeling and simulations have increased. Early modeling and simulations used ad hoc methods and semiempirical models, which were of limited accuracy and only gave qualitative results and trends. In addition, the treatment of the environment was either completely neglected or treated with distance dependent dielectrics and/or simple continuum models. With the development of first the generalized gradient approximation (GGA), then hybrid exchange correlation functionals, and finally rigorous optimized effective potentials (OEPs) for both exchange and correlation, density functional methods are now fast approaching the accuracy of the highest levels of ab initio wave function quantum mechanics methods, but at a reduced computational cost, which has allowed modeling and simulation studies to be performed on larger and more complex systems. In addition, one has recently realized that the environment is not a background for the biophysical and biochemical events, but an active participant. Hence, the inclusion of the solvent, cations, anions, and spectator species are all important and fundamental and must be included, along with the molecules and/or molecular complexes, which were formerly thought to be the fundamental entities of interest. The use of spectroscopic methods has been the key to unraveling and understanding the complexity of quantum molecular biological events and processes. But the tools to use to probe the events and processes may influence what one is trying to measure and/or observe, especially when one uses X‐ray radiation, as has been observed in many cases. Hence, the combination of both many spectroscopic methods and simulations techniques has been the answer to how to best understand and interpret the results of many supposedly contradictory experimental results. By only including part of the system in the simulations, or using limited time, space, and radiation (energy) windows, one has only taken snapshots of the complex biological processes and then tried to tell the story. This is like taking a few frames from a movie and trying to determine the complete story line, an almost impossible task. In this review, we present some of our fundamental contributions to this field, include those of other groups, and finally present what we see as the future, in terms of both modeling quantum molecular biological methods, but also of further extending the modeling and simulation methods to even more complex biological, interpersonal and even societal events and interactions. Mathematics and modeling are only tools which can be used to try to understand and quantify the world around us. But we must always remember that we are developing models, and the ultimate use and utility of our models and methods is their ability to reproduce physical reality, with the inputs being the various physical observables that we can measure and determine.

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Loads of special authorship functions: Linear growth in the percentage of “equal first authors” and corresponding authors

2009

J. Am. Soc. Inf. Sci.

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We show that between 1999 and 2008 the percentage of articles with more than one corresponding author or with several authors that contributed equally, leading to so-called "equal first authors," has steadily been on the rise. Increasing numbers of corresponding authors and equally contributing authors may lead to increased stress on teamwork if not properly acknowledged in research evaluation exercises.

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The exchange-correlation potential in ab initio density functional theory

Cited by 171 publications

References 55 publications

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Quantum Molecular Biological Methods Using Density Functional Theory

Loads of special authorship functions: Linear growth in the percentage of “equal first authors” and corresponding authors

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