Werner, Hans-Joachim and Schuetz, Martin (2011) An efficient local coupled cluster method for accurate thermochemistry of large systems. JOURNAL OF CHEMICAL PHYSICS, 135 (14): 144116. ISSN 0021-9606,
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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]
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PLESSET 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; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Research Group Theoretical Chemistry > Prof. Dr. Martin Schütz |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 02 Jun 2020 06:09 |
| Last Modified: | 02 Jun 2020 06:09 |
| URI: | https://pred.uni-regensburg.de/id/eprint/19977 |
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