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%2F61989592%3A15310%2F23%3A73622875" target="_blank" >RIV/61989592:15310/23:73622875 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/full/10.1021/acs.jctc.3c00828" target="_blank" >https://pubs.acs.org/doi/full/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 H-2, the parametric H-2-H-2 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

—

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

—

OECD FORD branch

10403 - Physical chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

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

1549-9618

e-ISSN

1549-9626

Volume of the periodical

19

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