Explicitly correlated coupled cluster methods with pair-specific geminals

被引：244

作者：

Werner, Hans-Joachim ^{[1
]}

Knizia, Gerald ^{[1
]}

Manby, Frederick R. ^{[2
]}

机构：

[1] Univ Stuttgart, Inst Theoret Chem, D-70569 Stuttgart, Germany

[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

来源：

MOLECULAR PHYSICS | 2011年 / 109卷 / 03期

关键词：

explicit correlation; coupled-cluster; core-valence correlation; F12-methods; 2ND-ORDER PERTURBATION-THEORY; CARTESIAN GAUSSIAN FUNCTIONS; CONSISTENT BASIS-SETS; CONVERGENT BASIS-SETS; AUXILIARY BASIS-SETS; MAIN-GROUP ELEMENTS; MOLECULAR INTEGRALS; PSEUDOPOTENTIALS; ATOMS; FORMULATION;

D O I：

10.1080/00268976.2010.526641

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：

Explicitly correlated MP2-F12 and CCSD(T)-F12 methods with orbital-pair-specific Slater-type geminals are proposed. The fixed amplitude ansatz of Ten-no is used, and different exponents of the Slater geminal functions can be chosen for core-core, core-valence, and valence-valence pairs. This takes care of the different sizes of the correlation hole and leads to improved results when inner-shell orbitals are correlated. The complications and the extra computational cost as compared to corresponding calculations with a single geminal are minor. The improved accuracy of the method is demonstrated for spectroscopic properties of Br(2), As(2), Ga(2), Cu(2), GaCl, CuCl, and CuBr, where the d-orbitals are treated as core.

引用

页码：407 / 417

页数：11

共 52 条

[21] Implementation of the full explicitly correlated coupled-cluster singles and doubles model CCSD-F12 with optimally reduced auxiliary basis dependence [J].