Why Nondynamic Correlation Matters for ππ Stacking? Lessons from the Benzene Dimer
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Why Nondynamic Correlation Matters for ππ Stacking? Lessons from the Benzene Dimer
Original language description
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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Result continuities
Project
—
Continuities
O - Projekt operacniho programu
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
The Journal of Physical Chemistry Letters
ISSN
1948-7185
e-ISSN
—
Volume of the periodical
—
Issue of the periodical within the volume
42
Country of publishing house
US - UNITED STATES
Number of pages
7
Pages from-to
10982-10988
UT code for WoS article
001593143500001
EID of the result in the Scopus database
2-s2.0-105018673252