Assessment of random phase approximation and second-order Moller-Plesset perturbation theory for many-body interactions in solid ethane, ethylene, and acetylene

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F23%3A10468450" target="_blank" >RIV/00216208:11320/23:10468450 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=a9MV-xx9I" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=a9MV-xx9I</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0142348" target="_blank" >10.1063/5.0142348</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Assessment of random phase approximation and second-order Moller-Plesset perturbation theory for many-body interactions in solid ethane, ethylene, and acetylene

Popis výsledku v původním jazyce

The relative energies of different phases or polymorphs of molecular solids can be small, less than a kilojoule/mol. A reliable description of such energy differences requires high-quality treatment of electron correlations, typically beyond that achievable by routinely applicable density functional theory (DFT) approximations. At the same time, high-level wave function theory is currently too computationally expensive. Methods employing an intermediate level of approximations, such as Moller-Plesset (MP) perturbation theory and the random phase approximation (RPA), are potentially useful. However, their development and application for molecular solids has been impeded by the scarcity of necessary benchmark data for these systems. In this work, we employ the coupled-cluster method with singles, doubles, and perturbative triples to obtain a reference-quality many-body expansion of the binding energy of four crystalline hydrocarbons with a varying p-electron character: ethane, ethene, and cubic and orthorhombic forms of acetylene. The binding energy is resolved into explicit dimer, trimer, and tetramer contributions, which facilitates the analysis of errors in the approximate approaches. With the newly generated benchmark data, we test the accuracy of MP2 and non-self-consistent RPA. We find that both of the methods poorly describe the non-additive many-body interactions in closely packed clusters. Using different DFT input states for RPA leads to similar total binding energies, but the many-body components strongly depend on the choice of the exchange-correlation functional.

Název v anglickém jazyce

Assessment of random phase approximation and second-order Moller-Plesset perturbation theory for many-body interactions in solid ethane, ethylene, and acetylene

Popis výsledku anglicky

The relative energies of different phases or polymorphs of molecular solids can be small, less than a kilojoule/mol. A reliable description of such energy differences requires high-quality treatment of electron correlations, typically beyond that achievable by routinely applicable density functional theory (DFT) approximations. At the same time, high-level wave function theory is currently too computationally expensive. Methods employing an intermediate level of approximations, such as Moller-Plesset (MP) perturbation theory and the random phase approximation (RPA), are potentially useful. However, their development and application for molecular solids has been impeded by the scarcity of necessary benchmark data for these systems. In this work, we employ the coupled-cluster method with singles, doubles, and perturbative triples to obtain a reference-quality many-body expansion of the binding energy of four crystalline hydrocarbons with a varying p-electron character: ethane, ethene, and cubic and orthorhombic forms of acetylene. The binding energy is resolved into explicit dimer, trimer, and tetramer contributions, which facilitates the analysis of errors in the approximate approaches. With the newly generated benchmark data, we test the accuracy of MP2 and non-self-consistent RPA. We find that both of the methods poorly describe the non-additive many-body interactions in closely packed clusters. Using different DFT input states for RPA leads to similar total binding energies, but the many-body components strongly depend on the choice of the exchange-correlation functional.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

R - Projekt Ramcoveho programu EK

Rok uplatnění

2023

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

158

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

18

Strana od-do

144119

Kód UT WoS článku

000971803700005

EID výsledku v databázi Scopus

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