Vibrational tunneling spectra of molecules with asymmetric wells: a combined vibrational configuration interaction and instanton approach

TL;DR

This paper introduces a combined vibrational configuration interaction and instanton approach to efficiently compute vibrational tunneling spectra in molecules with multiple, asymmetric wells, especially where quantum methods are computationally expensive.

Contribution

The paper develops a novel method integrating VSCF/VCI with semiclassical instanton theory for accurate vibrational spectra of asymmetric multi-well molecules.

Findings

Validated on a double-well model and malonaldehyde.

Accurately computed spectra for asymmetrically deuterated malonaldehyde.

Applicable to water clusters with minimal computational cost.

Abstract

A combined approach that uses the vibrational self-consistent field (VSCF) and vibrational configuration interaction (VCI) method together with the semiclassical instanton theory was developed to study vibrational tunneling spectra of molecules with multiple wells. The method can be applied to calculate low-lying vibrational states in the systems with arbitrary number of wells, which are not necessarily related by a symmetry operation. It is particularly suited to systems in which the wells are separated by large potential barriers and tunneling splittings are small, so that the exact quantum-mechanical methods come at a prohibitive computational cost. The accuracy of the method was tested on a two-dimensional double-well model system and on malonaldehyde, and the results were compared with the exact quantum-mechanical calculations. The method was subsequently applied to the asymmetrically deuterated malonaldehyde, which has non-degenerate vibrational frequencies in the two wells. The spectrum is obtained at a cost of single-well VSFC/VCI calculations. The interactions between states of different wells are computed semiclassically at a comparatively negligible computational cost. The method is particularly suited to the computation and assignment of spectra in the studies of water clusters.