Coupled-cluster methods including noniterative corrections for quadruple excitations.
A new method is presented for treating the effects of quadruple excitations in coupled-cluster theory. In the approach, quadruple excitation contributions are computed from a formula based on a non-Hermitian perturbation theory analogous to that used previously to justify the usual noniterative triples correction used in the coupled cluster singles and doubles method with a perturbative treatment of the triple excitations (CCSD(T)). The method discussed in this paper plays a parallel role in improving energies obtained with the full coupled-cluster singles, doubles, and triples method (CCSDT) by adding a perturbative treatment of the quadruple excitations (CCSDT(Q)). The method is tested for an extensive set of examples, and is shown to provide total energies that compare favorably with those obtained with the full singles, doubles, triples, and quadruples (CCSDTQ) method.
Bomble
Yannick J
YJ
Institute for Theoretical Chemistry, Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, USA. ybomble@mail.utexas.edu
Stanton
John F
JF
Kállay
Mihály
M
Gauss
Jürgen
J