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Werner, Hans-Joachim ; Schütz, Martin

An efficient local coupled cluster method for accurate thermochemistry of large systems

Werner, Hans-Joachim und Schütz, Martin (2011) An efficient local coupled cluster method for accurate thermochemistry of large systems. Journal of Chemical Physics 135 (14), S. 144116.

Veröffentlichungsdatum dieses Volltextes: 12 Dez 2011 08:36
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.22923


Zusammenfassung

An efficient local coupled cluster method with single and double excitation operators and perturbative treatment of triple excitations [DF-LCCSD(T)] is described. All required two-electron integrals are evaluated using density fitting approximations. These have a negligible effect on the accuracy but reduce the computational effort by 1-2 orders of magnitude, as compared to standard ...

An efficient local coupled cluster method with single and double excitation operators and perturbative treatment of triple excitations [DF-LCCSD(T)] is described. All required two-electron integrals are evaluated using density fitting approximations. These have a negligible effect on the accuracy but reduce the computational effort by 1-2 orders of magnitude, as compared to standard integral-direct methods. Excitations are restricted to local subsets of non-orthogonal virtual orbitals (domain approximation). Depending on distance criteria, the correlated electron pairs are classified into strong, close, weak, and very distant pairs. Only strong pairs, which typically account for more than 90% of the correlation energy, are optimized in the LCCSD treatment. The remaining close and weak pairs are approximated by LMP2 (local second-order Moller-Plesset perturbation theory); very distant pairs are neglected. It is demonstrated that the accuracy of this scheme can be significantly improved by including the close pair LMP2 amplitudes in the LCCSD equations, as well as in the perturbative treatment of the triples excitations. Using this ansatz for the wavefunction, the evaluation and transformation of the two-electron integrals scale cubically with molecular size. If local density fitting approximations are activated, this is reduced to linear scaling. The LCCSD iterations scale quadratically, but linear scaling can be achieved by neglecting some terms involving contractions of single excitations. The accuracy and efficiency of the method is systematically tested using various approximations, and calculations for molecules with up to 90 atoms and 2636 basis functions are presented. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3641642]



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftJournal of Chemical Physics
Verlag:AMER INST PHYSICS
Ort der Veröffentlichung:MELVILLE
Band:135
Nummer des Zeitschriftenheftes oder des Kapitels:14
Seitenbereich:S. 144116
Datum2011
InstitutionenChemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Arbeitskreis Theoretische Chemie (Theoretical Chemistry) > Prof. Dr. Martin Schütz
Identifikationsnummer
WertTyp
10.1063/1.3641642DOI
Klassifikation
NotationArt
31.15.bwPACS
31.15.xpPACS
31.15.V-PACS
31.15.E-PACS
33.15.BhPACS
Stichwörter / KeywordsPLESSET PERTURBATION-THEORY; ELECTRON CORRELATION METHODS; DENSITY FITTING APPROXIMATIONS; ANALYTICAL ENERGY GRADIENTS; AUXILIARY BASIS-SETS; TRIPLES CORRECTION T; ATOMIC ORBITAL BASIS; CONFIGURATION-INTERACTION; FUNCTIONAL THEORY; MP2 CALCULATIONS;
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-229239
Dokumenten-ID22923

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