Why Nondynamic Correlation Matters for ππ Stacking? Lessons from the Benzene Dimer

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61988987%3A17310%2F25%3AA2603C4J" target="_blank" >RIV/61988987:17310/25:A2603C4J - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpclett.5c02576" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpclett.5c02576</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.5c02576" target="_blank" >10.1021/acs.jpclett.5c02576</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Why Nondynamic Correlation Matters for ππ Stacking? Lessons from the Benzene Dimer

Popis výsledku v původním jazyce

Two leading methods for benchmarking ππ interactions are fixed-node diffusion Monte Carlo (DMC) and coupled cluster with singles, doubles, and perturbative triples [CCSD(T)]. The parallel-displaced benzene dimer (BZPD) is a key model for assessing the performance of theoretical approaches in describing these interactions. Reference calculations, symmetry-adapted perturbation theory, and correlation energy decompositions highlight the subtle but critical role of weak nondynamic correlation effects in achieving benchmark interaction energies for BZPD. While single-determinant DMC (SDDMC), using nodes from DFT or Hartree–Fock, performs well for many noncovalent systems, our analysis shows that neglecting weak nondynamic correlations in mean-field trial wave functions leads to systematic underbinding in SDDMC energy differences, in contrast to CCSD(T)/CBS results. These findings underscore the limitations of SDDMC for describing ππ interactions and emphasize the need for improved nodal descriptions to establish DMC as a reliable benchmark method for larger complexes.

Název v anglickém jazyce

Why Nondynamic Correlation Matters for ππ Stacking? Lessons from the Benzene Dimer

Popis výsledku anglicky

Two leading methods for benchmarking ππ interactions are fixed-node diffusion Monte Carlo (DMC) and coupled cluster with singles, doubles, and perturbative triples [CCSD(T)]. The parallel-displaced benzene dimer (BZPD) is a key model for assessing the performance of theoretical approaches in describing these interactions. Reference calculations, symmetry-adapted perturbation theory, and correlation energy decompositions highlight the subtle but critical role of weak nondynamic correlation effects in achieving benchmark interaction energies for BZPD. While single-determinant DMC (SDDMC), using nodes from DFT or Hartree–Fock, performs well for many noncovalent systems, our analysis shows that neglecting weak nondynamic correlations in mean-field trial wave functions leads to systematic underbinding in SDDMC energy differences, in contrast to CCSD(T)/CBS results. These findings underscore the limitations of SDDMC for describing ππ interactions and emphasize the need for improved nodal descriptions to establish DMC as a reliable benchmark method for larger complexes.

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

2025

Kód důvěrnosti údajů

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

Název periodika

The Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

—

Číslo periodika v rámci svazku

42

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

10982-10988

Kód UT WoS článku

001593143500001

EID výsledku v databázi Scopus

2-s2.0-105018673252