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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Svazek periodika

19

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

8147-8155

Kód UT WoS článku

001110556200001

EID výsledku v databázi Scopus

2-s2.0-85178021573