Random-phase approximation vs Møller-Plesset perturbation theory for many-body energy contributions of hydrogen-bonded molecular solids
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F25%3A10508343" target="_blank" >RIV/00216208:11320/25:10508343 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=g6jf6.eiAa" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=g6jf6.eiAa</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1063/5.0292113" target="_blank" >10.1063/5.0292113</a>
Alternative languages
Result language
angličtina
Original language name
Random-phase approximation vs Møller-Plesset perturbation theory for many-body energy contributions of hydrogen-bonded molecular solids
Original language description
The fragment-based approach is a promising strategy for applying correlated-wavefunction methods to lattice energies of molecular solids. A key requirement is the efficient inclusion of the long-distance and nonadditive contributions to the many-body expansion (MBE) of the lattice energy. This is especially important in crystals of polar molecules, where MBE converges slowly with distance. In this context, we compare the simplest coupled-cluster approach-the random-phase approximation (RPA)-against the well-established methodology of M & oslash;ller-Plesset (MP) perturbation theory. Using the examples of solid ammonia, methanol, and formic acid, we show that the RPA with singles corrections based on the Kohn-Sham (KS) Perdew-Burke-Ernzerhof (PBE) orbitals yields near-benchmark accuracy for the two-body contributions. However, for any PBE-based variant of RPA, the three- and four-body contributions suffer from artifacts. For the nonadditive terms, the Hartree-Fock (HF) orbitals appear necessary. In fact, we find that the HF-based RPA with additional corrections recovers the nonadditive interactions about as accurately as the more expensive MP2.5 method. This is a departure from the typical KS-based RPA and an indication that the HF-based RPA can serve as an alternative to the usual MP methods in accurate approximations of the crystal lattice energy.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10302 - Condensed matter physics (including formerly solid state physics, supercond.)
Result continuities
Project
<a href="/en/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Advanced MUltiscaLe materials for key Enabling Technologies</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
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
Journal of Chemical Physics
ISSN
0021-9606
e-ISSN
1089-7690
Volume of the periodical
163
Issue of the periodical within the volume
22
Country of publishing house
US - UNITED STATES
Number of pages
14
Pages from-to
224105
UT code for WoS article
001634622500001
EID of the result in the Scopus database
2-s2.0-105024066483