Unveiling hidden dynamic correlations in CASSCF correlation energies by Hartree–Fock nodes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61988987%3A17310%2F24%3AA25038IQ" target="_blank" >RIV/61988987:17310/24:A25038IQ - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.aip.org/jcp/article/161/11/114112/3312877/Unveiling-hidden-dynamic-correlations-in-CASSCF" target="_blank" >https://pubs.aip.org/jcp/article/161/11/114112/3312877/Unveiling-hidden-dynamic-correlations-in-CASSCF</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0223733" target="_blank" >10.1063/5.0223733</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Unveiling hidden dynamic correlations in CASSCF correlation energies by Hartree–Fock nodes

Popis výsledku v původním jazyce

We have recently introduced an original method for sharply partitioning the correlation energy into dynamic and non-dynamic contributions. This method is based on the node of the Hartree–Fock (HF) Slater determinant and the stochastic projector fixed-node diffusion Monte Carlo (FNDMC) method [Šulka et al., J. Chem. Theory Comput. 19, 8147 (2023)]. This approach addresses the challenge of dissecting correlation energy in quantum chemistry. Here, we present the first application of this technique to explore CASSCF correlation energy contributions in selected molecular systems such as BH, FH, F2, and H2–H2. The results show that correlation energies derived from the full-valence active space CASSCF method, often believed to describe mostly non-dynamic correlation effects, contain an extraneous, unwanted, system-dependent component that belongs to the dynamic correlation energy. The findings suggest that the new HF-node/FNDMC-based electron correlation energy decomposition method provides a useful complementary tool, enabling the detection of inherent challenges in distinguishing between dynamic and non-dynamic contributions to correlation energies within methods where precise dissection of these effects is not possible.

Název v anglickém jazyce

Unveiling hidden dynamic correlations in CASSCF correlation energies by Hartree–Fock nodes

Popis výsledku anglicky

We have recently introduced an original method for sharply partitioning the correlation energy into dynamic and non-dynamic contributions. This method is based on the node of the Hartree–Fock (HF) Slater determinant and the stochastic projector fixed-node diffusion Monte Carlo (FNDMC) method [Šulka et al., J. Chem. Theory Comput. 19, 8147 (2023)]. This approach addresses the challenge of dissecting correlation energy in quantum chemistry. Here, we present the first application of this technique to explore CASSCF correlation energy contributions in selected molecular systems such as BH, FH, F2, and H2–H2. The results show that correlation energies derived from the full-valence active space CASSCF method, often believed to describe mostly non-dynamic correlation effects, contain an extraneous, unwanted, system-dependent component that belongs to the dynamic correlation energy. The findings suggest that the new HF-node/FNDMC-based electron correlation energy decomposition method provides a useful complementary tool, enabling the detection of inherent challenges in distinguishing between dynamic and non-dynamic contributions to correlation energies within methods where precise dissection of these effects is not possible.

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

2024

Kód důvěrnosti údajů

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

Název periodika

JOURNAL OF CHEMICAL PHYSICS

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

—

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

—

Kód UT WoS článku

001314608300001

EID výsledku v databázi Scopus

2-s2.0-85204417320