Unraveling rotation-vibration mixing in highly fluxional molecules using diffusion Monte Carlo: applications to H3+ and H3O+.

ABSTRACT

A thorough examination of the use of fixed-node diffusion Monte Carlo for the study of rotation-vibration mixing in systems that undergo large amplitude vibrational motions is reported. Using H(3)(+) as a model system, the overall accuracy of the method is tested by comparing the results of these calculations with those from converged variational calculations. The effects of the presence of a large amplitude inversion mode on rotation-vibration mixing are considered by comparing the H(3)(+) results with those for H(3)O(+). Finally, analysis of the results of the fixed-node diffusion Monte Carlo calculations performed in different nodal regions is found to provide clear indications of when some of the methodology's underlying assumptions are breaking down as well as provide physical insights into the form of the rotation-vibration coupling that is most likely responsible.