6533b85ffe1ef96bd12c1d93

RESEARCH PRODUCT

Coupled-cluster methods including noniterative corrections for quadruple excitations

Yannick J. BombleMihály KállayJohn F. StantonJürgen Gauss

subject

Set (abstract data type)PhysicsCoupled clusterExcited stateQuantum electrodynamicsGeneral Physics and AstronomyPerturbation theory (quantum mechanics)Physical and Theoretical ChemistryExcitation

description

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.

yearjournalcountryeditionlanguage
2005-08-20The Journal of Chemical Physics
https://doi.org/10.1063/1.1950567