A state-specific multireference coupled-cluster method based on the bivariational principle.

Abstract

A state-specific multireference coupled-cluster (MRCC) method based on Arponen's bivariational principle is presented, the bivar-MRCC method. The method is based on single-reference theory and therefore has a relatively straightforward formulation and modest computational complexity. The main difference from established methods is the bivariational formulation, in which independent parameterizations of the wave function (ket) and its complex conjugate (bra) are made. Importantly, this allows manifest multiplicative separability of the state (exact in the extended bivar-MRECC version of the method and approximate otherwise), and additive separability of the energy, while preserving polynomial scaling of the working equations. A feature of the bivariational principle is that the formal bra and ket references can be included as bivariational parameters, which eliminates much of the bias toward the formal reference. A pilot implementation is described, and extensive benchmark calculations on several standard problems are performed. The results from the bivar-MRCC method are comparable to established state-specific multireference methods. Considering the relative affordability of the bivar-MRCC method, it may become a practical tool for non-experts.