Excited states with internally contracted multireference coupled-cluster linear response theory.

2014

In this paper, the linear response (LR) theory for the variant of internally contracted multireference coupled cluster (ic-MRCC) theory described by Hanauer and Kohn [J. Chem. Phys. 134, 204211 (2011)] has been formulated and implemented for the computation of the excitation energies relative to a ground state of pronounced multireference character. We find that straightforward application of the linear-response formalism to the time-averaged ic-MRCC Lagrangian leads to unphysical second-order poles. However, the coupling matrix elements that cause this behavior are shown to be negligible whenever the internally contracted approximation as such is justified. Hence, for the numerical impleme…