Orbital-Optimized MP3 and MP2.5 with Density-Fitting and Cholesky Decomposition Approximations

被引：42

作者：

Bozkaya, Ugur ^{[1
]}

机构：

[1] Hacettepe Univ, Dept Chem, TR-06800 Ankara, Turkey

来源：

JOURNAL OF CHEMICAL THEORY AND COMPUTATION | 2016年 / 12卷 / 03期

关键词：

COUPLED-CLUSTER THEORY; PLESSET PERTURBATION-THEORY; CORRELATED MOLECULAR CALCULATIONS; NONCOVALENT INTERACTION ENERGIES; EXTENDED KOOPMANS THEOREM; GAUSSIAN-BASIS SETS; DOUBLES MODEL; AB-INITIO; RESPONSE THEORY; SPIN-COMPONENT;

D O I：

10.1021/acs.jctc.5b01128

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Efficient implementations of the orbital-optimized MP3 and MP2.5 methods with the density-fitting (DF-OMP3 and DF-OMP2.5) and Cholesky decomposition (CD-OMP3 and CD-OMP2.5) approaches are presented. The DF/CD-OMP3 and DF/CD-OMP2.5 methods are applied to a set of alkanes to compare the computational cost with the conventional orbital-optimized MP3 (OMP3) [Bozkaya J. Chem. Phys. 2011, 135, 224103] and the orbital-optimized MP2.5 (OMP2.5) [Bozkaya and Sherrill J. Chem. Phys. 2014, 141, 204105]. Our results demonstrate that the DF-OMP3 and DF-OMP2.5, methods provide considerably lower computational costs than OMP3 and OMP2.5. Further application results show that the orbital-optimized methods are very helpful for the study of open-shell noncovalent interactions, aromatic bond dissociation energies, and hydrogen transfer reactions. We conclude that the DF-OMP3 and DF-OMP2.5 methods are very promising for molecular systems with challenging electronic structures.

引用

页码：1179 / 1188

页数：10

共 72 条

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