Assessment of the single-root multireference Brillouin-Wigner coupled-cluster method: Test calculations on CH_2, SiH_2, and twisted ethylene

摘要

Recently developed single-root multireference Brillouin-Wigner coupled-cluster (MR BWCC) theory, which belongs to a broad family of state-selective multireference coupled-cluster methods, has been implemented in the ACES II program package at the CCSD level of approximation. The method represents a new approach to quasidegenerate problems, which is able to continuously switch between the single-reference CC in a nondegenerate situation and the Hilbert-space MRCC in a degenerate case. An assessment of the method has been carried out by means of a comparison with the full configuration interaction (CI) treatments of CH_2, SiH_2, and twisted ethylene diradicals. The problem of size-extensivity is discussed.