Implementation of the CCSD(T)-F12 method using cusp conditions

被引:71
作者
Bokhan, Denis [1 ,2 ]
Ten-No, Seiichiro [1 ,2 ]
Noga, Jozef [3 ,4 ]
机构
[1] Nagoya Univ, Grad Sch Informat Sci, Chikusa Ku, Nagoya, Aichi 4648601, Japan
[2] Japan Sci & Technol Agcy, CREST, Kawaguchi, Saitama 3320012, Japan
[3] Comenius Univ, Fac Nat Sci, Dept Phys & Theoret Chem, SK-84215 Bratislava, Slovakia
[4] Slovak Acad Sci, Inst Inorgan Chem, SK-84536 Bratislava, Slovakia
关键词
D O I
10.1039/b803426p
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
The explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)-F12) is implemented using the cusp conditions. Numerical tests for a set of 16 molecules have shown agreement of correlation energies within 1 mE(h) between the cusp-condition and fully-optimized CCSD(T)-F12 methods. Benchmark calculations on 13 chemical reactions with the cusp-condition CCSD(T)-F12 method reproduce experimental enthalpies within 2 kJ mol(-1). It is also shown that regular unitary-invariant ansatz cannot exactly satisfy singlet and triplet cusp conditions in open-shell situations. We present an extended ansatz which can handle both conditions exactly.
引用
收藏
页码:3320 / 3326
页数:7
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