Analytic gradient for the multireference Brillouin-Wigner coupled cluster method and for the state-universal multireference coupled cluster method

Abstract

We present the analytic gradient theory and its pilot implementation for the multireference Brillouin-Wigner coupled cluster (BWCC) method and for the state-universal multireference coupled cluster method. The analytic gradient has been derived for three cases: (i) BWCC method without a size-extensivity correction, (ii) BWCC method with the iterative size-extensivity correction, and (iii) for the rigorously size-extensive state-universal method. The pilot implementation is based on full-configuration interaction expansions and is presently limited to single and double excitation levels; however, the resulting equations are general. For BWCC methods, they also do not contain terms explicitly mixing amplitudes of different reference configurations and can thus be implemented in an efficient way. The analytic gradients have been verified with respect to numerically computed ones on the example of CH2 molecule, and geometry optimizations of CH2 and SiH2 have been carried out.