Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F21%3A10436184" target="_blank" >RIV/00216208:11320/21:10436184 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=.RJH3p1kxz" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=.RJH3p1kxz</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.0c00966" target="_blank" >10.1021/acs.jctc.0c00966</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Popis výsledku v původním jazyce

The many-body expansion (MBE) of energies of molecular clusters or solids offers a way to detect and analyze errors of theoretical methods that could go unnoticed if only the total energy of the system was considered. In this regard, the interaction between the methane molecule and its enclosing dodecahedral water cage, CH4 center dot center dot center dot(H2O)(20), is a stringent test for approximate methods, including density functional theory (DFT) approximations. Hybrid and semilocal DFT approximations behave erratically for this system, with three- and four-body nonadditive terms having neither the correct sign nor magnitude. Here, we analyze to what extent these qualitative errors in different MBE contributions are conveyed to post-Kohn-Sham random-phase approximation (RPA), which uses approximate Kohn-Sham orbitals as its input. The results reveal a correlation between the quality of the DFT input states and the RPA results. Moreover, the renormalized singles energy (RSE) corrections play a crucial role in all orders of the many-body expansion. For dimers, RSE corrects the RPA underbinding for every tested Kohn-Sham model: generalized-gradient approximation (GGA), meta-GGA, (meta-)GGA hybrids, as well as the optimized effective potential at the correlated level. Remarkably, the inclusion of singles in RPA can also correct the wrong signs of three- and four-body nonadditive energies as well as mitigate the excessive higher-order contributions to the many-body expansion. The RPA errors are dominated by the contributions of compact clusters. As a workable method for large systems, we propose to replace those compact contributions with CCSD(T) energies and to sum up the remaining many-body contributions up to infinity with supermolecular or periodic RPA. As a demonstration of this approach, we show that for RPA(PBE0)+RSE it suffices to apply CCSD(T) to dimers and 30 compact, hydrogen-bonded trimers to get the methane-water cage interaction energy to within 1.6% of the reference value.

Název v anglickém jazyce

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Popis výsledku anglicky

The many-body expansion (MBE) of energies of molecular clusters or solids offers a way to detect and analyze errors of theoretical methods that could go unnoticed if only the total energy of the system was considered. In this regard, the interaction between the methane molecule and its enclosing dodecahedral water cage, CH4 center dot center dot center dot(H2O)(20), is a stringent test for approximate methods, including density functional theory (DFT) approximations. Hybrid and semilocal DFT approximations behave erratically for this system, with three- and four-body nonadditive terms having neither the correct sign nor magnitude. Here, we analyze to what extent these qualitative errors in different MBE contributions are conveyed to post-Kohn-Sham random-phase approximation (RPA), which uses approximate Kohn-Sham orbitals as its input. The results reveal a correlation between the quality of the DFT input states and the RPA results. Moreover, the renormalized singles energy (RSE) corrections play a crucial role in all orders of the many-body expansion. For dimers, RSE corrects the RPA underbinding for every tested Kohn-Sham model: generalized-gradient approximation (GGA), meta-GGA, (meta-)GGA hybrids, as well as the optimized effective potential at the correlated level. Remarkably, the inclusion of singles in RPA can also correct the wrong signs of three- and four-body nonadditive energies as well as mitigate the excessive higher-order contributions to the many-body expansion. The RPA errors are dominated by the contributions of compact clusters. As a workable method for large systems, we propose to replace those compact contributions with CCSD(T) energies and to sum up the remaining many-body contributions up to infinity with supermolecular or periodic RPA. As a demonstration of this approach, we show that for RPA(PBE0)+RSE it suffices to apply CCSD(T) to dimers and 30 compact, hydrogen-bonded trimers to get the methane-water cage interaction energy to within 1.6% of the reference value.

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

2021

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Svazek periodika

17

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

804-817

Kód UT WoS článku

000634678200018

EID výsledku v databázi Scopus

2-s2.0-85100007199