Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and Projector Augmented-wave methods

The direct random-phase approximation (dRPA) is used to calculate and compare atomization energies for the HEAT set and 10 selected molecules of the G2-1 set using both plane waves and Gaussian-type orbitals. We describe detailed procedures to obtain highly accurate and well converged results for th...

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Bibliographic Details
Published inarXiv.org
Main Authors Humer, Moritz, Harding, Michael E, Schlipf, Martin, Taheridehkordi, Amir, Sukurma, Zoran, Klopper, Wim, Kresse, Georg
Format Paper Journal Article
LanguageEnglish
Published Ithaca Cornell University Library, arXiv.org 31.08.2022
Subjects
Approximation
Atomizing
Correlation
Density functional theory
Exchanging
Mathematical analysis
Orbitals
Physics - Chemical Physics
Physics - Computational Physics
Plane waves
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Summary:The direct random-phase approximation (dRPA) is used to calculate and compare atomization energies for the HEAT set and 10 selected molecules of the G2-1 set using both plane waves and Gaussian-type orbitals. We describe detailed procedures to obtain highly accurate and well converged results for the projector augmented-wave (PAW) method as implemented in the Vienna Ab-initio Simulation Package (VASP) as well as the explicitly correlated dRPA-F12 method as implemented in the TURBOMOLE package. The two approaches agree within chemical accuracy (1 kcal/mol) for the atomization energies of all considered molecules, both for the exact exchange as well as for the dRPA. The root mean-square deviation is 0.41 kcal/mol for the exact exchange (evaluated using density functional theory orbitals) and 0.33 kcal/mol for exact exchange plus the random-phase approximation.
ISSN:2331-8422
DOI:10.48550/arxiv.2208.14726