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Schütz, Martin ; Yang, Jun ; Chan, Garnet Kin-Lic ; Manby, Frederick R. ; Werner, Hans-Joachim

The orbital-specific virtual local triples correction: OSV-L(T)

Schütz, Martin, Yang, Jun , Chan, Garnet Kin-Lic, Manby, Frederick R. und Werner, Hans-Joachim (2013) The orbital-specific virtual local triples correction: OSV-L(T). The Journal of Chemical Physics 138, 054109.

Veröffentlichungsdatum dieses Volltextes: 21 Okt 2016 11:13
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.34744


Zusammenfassung

A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schutz [J. Chem. Phys. 113, 9986 (2000)], the new scheme works without any ad hoc truncations of the virtual space to domains. A single threshold ...

A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schutz [J. Chem. Phys. 113, 9986 (2000)], the new scheme works without any ad hoc truncations of the virtual space to domains. A single threshold defines the pair and triple specific virtual spaces completely and automatically. It is demonstrated that the computational cost of the method scales linearly with molecular size. Employing the recommended threshold a similar fraction of the correlation energy is recovered as with the original PAO method at a somewhat lower cost. A benchmark for 52 reactions demonstrates that for reaction energies the intrinsic accuracy of the coupled cluster with singles and doubles excitations and a perturbative treatment of triples excitations method can be reached by OSV-local coupled cluster theory with singles and doubles and perturbative triples, provided a MP2 correction is applied that accounts for basis set incompleteness errors as well as for remaining domain errors. As an application example the interaction energies of the guanine-cytosine dimers in the Watson-Crick and stacked arrangements are investigated at the level of local coupled cluster theory with singles and doubles and perturbative triples. Based on these calculations we propose new complete-basis-set-limit estimates for these interaction energies at this level of theory. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789415]



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftThe Journal of Chemical Physics
Verlag:AMER INST PHYSICS
Ort der Veröffentlichung:MELVILLE
Band:138
Seitenbereich:054109
Datum2013
InstitutionenChemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Arbeitskreis Theoretische Chemie (Theoretical Chemistry) > Prof. Dr. Martin Schütz
Identifikationsnummer
WertTyp
10.1063/1.4789415DOI
Stichwörter / KeywordsELECTRON CORRELATION METHODS; PLESSET PERTURBATION-THEORY; COUPLED-CLUSTER THEORY; DNA-BASE PAIRS; CONFIGURATION-INTERACTION; BASIS-SETS; CHOLESKY DECOMPOSITIONS; CORRELATION ENERGIES; CORRECTION T; PNO-CI;
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-347444
Dokumenten-ID34744

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