Dynamic and Nondynamic Electron Correlation Energy Decomposition Based on the Node of the Hartree–Fock Slater Determinant

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61988987%3A17310%2F23%3AA2402NLL" target="_blank" >RIV/61988987:17310/23:A2402NLL - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/abs/10.1021/acs.jctc.3c00828" target="_blank" >https://pubs.acs.org/doi/abs/10.1021/acs.jctc.3c00828</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.3c00828" target="_blank" >10.1021/acs.jctc.3c00828</a>

Result language

angličtina

Original language name

Dynamic and Nondynamic Electron Correlation Energy Decomposition Based on the Node of the Hartree–Fock Slater Determinant

Original language description

Distinguishing between dynamic and nondynamic electron correlation energy is a fundamental concept in quantum chemistry. It can be challenging to make a clear distinction between the two types of correlation energy or to determine their actual contributions in specific cases using wave function theory. This is because both single-reference and multireference methods cover both types of correlation energy to some extent. Fixed-node diffusion quantum Monte Carlo (FNDMC) accurately covers dynamic correlations, but it is limited in overall accuracy by the node of the trial wave function. We introduce a methodology for partitioning an exact electron correlation energy into its dynamic and nondynamic components. This is accomplished by restricting a ground-state solution from sharing its node with a spin-restricted Hartree–Fock Slater determinant. The FNDMC method is used as a tool to conveniently project out a lowest-energy state obeying such a boundary condition. The proposed approach provides an unambiguous and useful procedure for separating electron correlation energy, as demonstrated on multiple systems, including the He atom, bond breaking of H2, the parametric H2–H2 system, the Be–Ne atomic series with low- and high-spin states for C, N, and O atoms, and small molecules such as BH, HF, and CO at both equilibrium and elongated configurations, respectively.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Project

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Continuities

O - Projekt operacniho programu

Publication year

2023

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9626

e-ISSN

—

Volume of the periodical

—

Issue of the periodical within the volume

22

Country of publishing house

US - UNITED STATES

Number of pages

9

Pages from-to

8147-8155

UT code for WoS article

001110556200001

EID of the result in the Scopus database

2-s2.0-85178021573