MAP: An MP2 Accuracy Predictor for Weak Interactions from Adiabatic Connection Theory

Vuckovic, Stefan; Fabiano, Eduardo; Gori‐Giorgi, Paola; Burke, Kieron

doi:10.1021/acs.jctc.0c00049

Cited by 16 publications

(60 citation statements)

References 59 publications

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“…The computational details are the same as in the supplementary material of Ref. 34, where we have used full configuration interaction (FCI) with an uncontracted augcc-pVTZ basis set to solve the λ-dependent Hamiltonian of Eq. (1) for the restricted HF case.…”

Section: Articlementioning

confidence: 99%

“…These interpolations can easily be corrected from their sizeconsistency error 30 and have been shown to also provide a diagnostic indicator for the accuracy of MP2 for non-covalent interactions. 34 Note that the Wilson-Levy 24 functional was also constructed by generalizing Wigner's original idea 35 of interpolating between weakand strong-interactions. Thus, there seems to be an indication that non-covalent interactions can be modeled in an accurate way by using the interpolation idea to build E HF c .…”

Section: Introductionmentioning

confidence: 99%

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Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms

Daas

Grossi

Vuckovic

et al. 2020

The Journal of Chemical Physics

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114

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Section: Articlementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms

Daas

Grossi

Vuckovic

et al. 2020

The Journal of Chemical Physics

Self Cite

114

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show abstract

“…[53]). At a more formal level, the adiabatic connection formalism that underpins the construction of the recently proposed HF-DHs [43,45,60] is different from the usual DFT adiabatic connection used to rationalize and build standard DHs [61,62].…”

Section: Can Double Hybrids Benefit From Hf-dft? Yes If Dc-dft Is App...mentioning

confidence: 99%

Density-corrected DFT explained: Questions and answers

Song¹,

Vuckovic²,

Sim³

et al. 2021

Preprint

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HF-DFT, the practice of evaluating approximate density functionals on Hartree-Fock densities, has long been used in testing density functional approximations. Density-corrected DFT (DC-DFT) is a general theoretical framework for identifying failures of density functional approximations by separating errors in a functional from errors in its self-consistent (SC) density. Most modern DFT calculations yield highly accurate densities, but important characteristic classes of calculation have large density-driven errors, including reaction barrier heights, electron affinities, radicals and anions in solution, dissociation of heterodimers, and even some torsional barriers. Here, the HF density (if not spin-contaminated) usually yields more accurate and consistent energies than those of the SC density. We use the term DC(HF)-DFT to indicate DC-DFT using HF densities only in such cases. A recent comprehensive study (J. Chem. Theory Comput. 2021, 17, 1368−1379 of HF-DFT led to many unfavorable conclusions. A re-analysis using DC-DFT shows that DC(HF)-DFT substantially improves DFT results precisely when SC densities are flawed.

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“…33,53,61,64,65 The lack of size-consistency of the ISI approach had been considered its main drawback, but a recent remarkably simple size-consistency correction (SCC) fixes this problem in an exact way, at least for systems dissociating into fragments with a non-degenerate ground state. 23,66 This SCC has been used for building functionals 23,66,67 in the DFT context, and has been already shown to be crucial for the accuracy of model MP AC curves (see Section S3 of Ref. 66) that can signal when an MP2 calculation is not reliable.…”

mentioning

confidence: 99%

“…66) that can signal when an MP2 calculation is not reliable. 66 The idea of this work is to use this approach, originally designed for the DFT AC, in the MP AC context to build accurate approximations to describe NCIs. The mentioned SCC 23 is also used throughout this work to restore size-consistency of our MP AC models.…”

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confidence: 99%

Noncovalent interactions from models for the Møller-Plesset adiabatic connection

Daas¹,

Fabiano²,

Sala³

et al. 2021

Preprint

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Given the omnipresence of non-covalent interactions (NCIs), their accurate simulations are of crucial importance across various scientific disciplines. Here we construct accurate models for the description of NCIs by an interpolation along the Møller-Plesset adiabatic connection (MP AC). Our interpolation approximates the correlation energy, by recovering MP2 at small coupling strengths and the correct large-coupling strength expansion of the MP AC, recently shown to be a functional of the Hartree-Fock density. Our models are size consistent for fragments with non-degenerate ground states, have the same cost as double hybrids and require no dispersion corrections to capture NCIs accurately. These interpolations greatly reduce large MP2 errors for typical πstacking complexes (e.g., benzene-pyridine dimers) and for the L7 dataset. They are also competitive with state-of-the-art dispersion enhanced functionals and can even significantly outperform them for a variety of datasets, such as CT7 and L7.

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MAP: An MP2 Accuracy Predictor for Weak Interactions from Adiabatic Connection Theory

Cited by 16 publications

References 59 publications

Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms

Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms

Density-corrected DFT explained: Questions and answers

Noncovalent interactions from models for the Møller-Plesset adiabatic connection

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