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%2F61988987%3A17310%2F23%3AA2402NLL" target="_blank" >RIV/61988987:17310/23:A2402NLL - isvavai.cz</a>

Výsledek na webu

<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>

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 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.

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 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

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

Projekt

—

Návaznosti

O - Projekt operacniho programu

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

1549-9626

e-ISSN

—

Svazek periodika

—

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