Tunneling splittings of vibrationally excited states using general instanton paths

TL;DR

This paper introduces a multidimensional semiclassical instanton method to accurately compute tunneling splittings in vibrationally excited states of molecules, extending previous theories to asymmetric paths and improving estimates for complex systems.

Contribution

It develops a generalized instanton-based semiclassical approach for vibrationally excited states, enabling efficient and accurate tunneling splitting calculations in multi-well molecular systems.

Findings

Method successfully applied to water dimer and model potentials.

Improved splitting estimates with new terms in wavefunction description.

Applicable to mid-sized molecules with full dimensionality.

Abstract

A multidimensional semiclassical method for calculating tunneling splittings in vibrationally excited states of molecules using Cartesian coordinates is developed. It is an extension of the theory by Mil'nikov and Nakamura [$\textit{ J. Chem. Phys.}$ $\textbf{122}$, $124311$ $(2005)$] to asymmetric paths that are necessary for calculating tunneling splitting patterns in multi-well systems, such as water clusters. Additionally, new terms are introduced in the description of the semiclassical wavefunction that drastically improve the splitting estimates for certain systems. The method is based on the instanton theory and builds the semiclassical wavefunction of the vibrationally excited states from the ground-state instanton wavefunction along the minimum action path and its harmonic neighborhood. The splittings of excited states are thus obtained at a negligible added numerical effort. The cost is concentrated, as for the ground-state splittings, in the instanton path optimization and the hessian evaluation along the path. The method can thus be applied without modification to many mid-sized molecules in full dimensionality and in combination with on-the-fly evaluation of electronic potentials. The tests were performed on several model potentials and on the water dimer.