Explicitly correlated coupled cluster methods with pair-specific geminals

被引：241

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

收藏

页码：407 / 417

页数：11

相关论文

共 52 条

[1] A simple and efficient CCSD(T)-F12 approximation [J].

Adler, Thomas B. ;

Knizia, Gerald ;

Werner, Hans-Joachim .

JOURNAL OF CHEMICAL PHYSICS, 2007, 127 (22)

[2] Local explicitly correlated second-order perturbation theory for the accurate treatment of large molecules [J].

Adler, Thomas B. ;

Werner, Hans-Joachim ;

Manby, Frederick R. .

JOURNAL OF CHEMICAL PHYSICS, 2009, 130 (05)

[3] A simple algebraic derivation of the Obara-Saika scheme for general two-electron interaction potentials [J].

Ahlrichs, R .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2006, 8 (26) :3072-3077

[4] Efficient evaluation of three-center two-electron integrals over Gaussian functions [J].

Ahlrichs, R .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2004, 6 (22) :5119-5121

[5] Explicitly correlated second-order perturbation theory calculations on molecules containing heavy main-group elements [J].

Bischoff, Florian A. ;

Hoefener, Sebastian ;

Gloess, Andreas ;

Klopper, Wim .

THEORETICAL CHEMISTRY ACCOUNTS, 2008, 121 (1-2) :11-19

[6] Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited [J].

Dunning, TH ;

Peterson, KA ;

Wilson, AK .

JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (21) :9244-9253

[7] Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac-Hartree-Fock data [J].

Figgen, D ;

Rauhut, G ;

Dolg, M ;

Stoll, H .

CHEMICAL PHYSICS, 2005, 311 (1-2) :227-244

[8] Coupled-cluster theory with simplified linear-r12 corrections:: The CCSD(R12) model -: art. no. 084107 [J].

Fliegl, H ;

Klopper, W ;

Hättig, C .

JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (08)

[9] Inclusion of the (T) triples correction into the linear-r12 corrected coupled-cluster model CCSD(R12) [J].

Fliegl, Heike ;

Hattig, Christof ;

Klopper, Wim .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2006, 106 (11) :2306-2317

[10] Communications: Accurate and efficient approximations to explicitly correlated coupled-cluster singles and doubles, CCSD-F12 [J].

Haettig, Christof ;

Tew, David P. ;

Koehn, Andreas .

JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (23)

← 1 2 3 4 5 6 →