Contributions beyond direct random-phase approximation in the binding energy of solid ethane, ethylene, and acetylene

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F24%3A10490010" target="_blank" >RIV/00216208:11320/24:10490010 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=LSgHueOjmR" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=LSgHueOjmR</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0207090" target="_blank" >10.1063/5.0207090</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Contributions beyond direct random-phase approximation in the binding energy of solid ethane, ethylene, and acetylene

Popis výsledku v původním jazyce

The random-phase approximation (RPA) includes a subset of higher than second-order correlation-energy contributions, but stays in the same complexity class as the second-order Moller-Plesset perturbation theory (MP2) in both Gaussian-orbital and plane-wave codes. This makes RPA a promising ab initio electronic structure approach for the binding energies of molecular crystals. Still, some issues stand out in practical applications of RPA. Notably, compact clusters of nonpolar molecules are poorly described, and the interaction energies strongly depend on the reference single-determinant state. Using the many-body expansion of the binding energy of a crystal, we investigate those issues and the effect of beyond-RPA corrections. We find the beneficial effect of quartic-scaling exchange and non-ring coupled-cluster doubles corrections. The nonadditive interactions in compact trimers of molecules are improved by using the self-consistent Hartree-Fock orbitals instead of the usual Kohn-Sham states, but this kind of orbital input also leads to underestimated dimer energies. Overall, a substantial improvement over the RPA with a renormalized singles approach is possible at a modest quartic-scaling cost, which encourages further research into additional RPA corrections. (c) 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(https://creativecommons.org/licenses/by/4.0/).

Název v anglickém jazyce

Contributions beyond direct random-phase approximation in the binding energy of solid ethane, ethylene, and acetylene

Popis výsledku anglicky

The random-phase approximation (RPA) includes a subset of higher than second-order correlation-energy contributions, but stays in the same complexity class as the second-order Moller-Plesset perturbation theory (MP2) in both Gaussian-orbital and plane-wave codes. This makes RPA a promising ab initio electronic structure approach for the binding energies of molecular crystals. Still, some issues stand out in practical applications of RPA. Notably, compact clusters of nonpolar molecules are poorly described, and the interaction energies strongly depend on the reference single-determinant state. Using the many-body expansion of the binding energy of a crystal, we investigate those issues and the effect of beyond-RPA corrections. We find the beneficial effect of quartic-scaling exchange and non-ring coupled-cluster doubles corrections. The nonadditive interactions in compact trimers of molecules are improved by using the self-consistent Hartree-Fock orbitals instead of the usual Kohn-Sham states, but this kind of orbital input also leads to underestimated dimer energies. Overall, a substantial improvement over the RPA with a renormalized singles approach is possible at a modest quartic-scaling cost, which encourages further research into additional RPA corrections. (c) 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(https://creativecommons.org/licenses/by/4.0/).

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

R - Projekt Ramcoveho programu EK

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

160

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

224101

Kód UT WoS článku

001244483600006

EID výsledku v databázi Scopus

2-s2.0-85195627537