Computation of expectation values from vibrational coupled-cluster at the two-mode coupling level

Abstract

In this work we show how the vibrational coupled-cluster method at the two-mode coupling level can be used to calculate zero-point vibrational averages of properties. A technique is presented, where any expectation value can be calculated using a single set of Lagrangian multipliers computed solving iteratively a single linear set of equations. Sample calculations are presented which show that the resulting algorithm scales only with the third power of the number of modes, therefore making large systems accessible. Moreover, we present applications to water, pyrrole, and para-nitroaniline.