Time-dependent coupled cluster with orthogonal adaptive basis functions: General formalism and application to the vibrational problem

Abstract: We derive equations of motion for bivariational wave functions with orthogonal adaptive basis sets and specialize the formalism to the coupled cluster ansatz. The equations are related to the biorthogonal case in a transparent way, and similarities and differences are analyzed. We show that the amplitude equations are identical in the orthogonal and biorthogonal formalisms, while the linear equations that determined the basis set time evolution differ by symmetrization. Applying the orthogonal framework to the nuclear dynamics problem, we introduce and implement the orthogonal time-dependent modal vibrational coupled cluster (oTDMVCC) method and benchmark it against exact reference results for four triatomic molecules as well as a 5D trans-bithiophene model. We confirm numerically that the biorthogonal TDMVCC hierarchy converges to the exact solution, while oTDMVCC does not. The differences between TDMVCC and oTDMVCC are found to be small for three of the five cases, but we also identify one case where the formal deficiency of the oTDMVCC approach results in clear and visible errors relative to the exact result. For the remaining example, oTDMVCC exhibits rather modest but visible errors.