Perturbative triple excitation corrections to coupled cluster singles and doubles excitation energies

The contributions from various excitation levels to excitation energies calculated within a coupled cluster framework are analyzed in terms of order in the fluctuation potential. In particular, the role of triple excitations is considered, focusing on their importance for describing excitations of single and double replacement dominated character. Several noniterative triples corrections to the coupled cluster singles and doubles (CCSD) excitation energies are proposed. In the CCSDR(3) approach, which is a noniterative analog to the recently proposed iterative CC3 model, single replacement dominated excitations are correct through third order in the fluctuation potential, and double replacement dominated excitations are correct through second order. The performance of CCSDR(3) is compared to other noniterative and iterative triples models in benchmark calculations on CH+, Ne, BH, and CH2. © 1996 American Institute of Physics