Exact quantum dynamics of methanol: full-dimensional ab initio potential energy surface of spectroscopic quality and variational vibrational states

TL;DR

This paper presents a full-dimensional ab initio potential energy surface and exact quantum dynamics calculations for methanol, enabling accurate prediction of its vibrational spectra and tunnelling splittings relevant to astrochemistry and fundamental physics.

Contribution

It introduces a spectroscopic-quality potential energy surface and variational vibrational calculations for methanol, achieving near-experimental accuracy and facilitating detailed rovibrational analysis.

Findings

Vibrational band origins agree within 5 cm$^{-1}$ of experiment

Computed tunnelling splittings and vibrational energies are highly accurate

Method enables detailed simulation of methanol's rovibrational spectra

Abstract

The methanol molecule is a sensitive probe of astrochemistry, astrophysics, and fundamental physics. The first-principles elucidation and prediction of its rotation-torsional-vibrational motions are enabled in this work by the computation of a full-dimensional, \emph{ab initio} potential energy surface (PES) and numerically exact quantum dynamics. An active-learning approach is used to sample explicitly correlated coupled-cluster electronic energies, and the datapoints are fitted with permutationally invariant polynomials to obtain a spectroscopic-quality PES representation. Variational vibrational energies and corresponding tunnelling splittings are computed up to the first overtone of the C-O stretching mode by direct numerical solution of the vibrational Schr\"odinger equation with optimal internal coordinates and efficient basis and grid truncation techniques. As a result, the computed vibrational band origins finally agree with experiment within 5 cm$^{-1}$, allowing for the exploration of the large-amplitude quantum mechanical motion and tunnelling splittings coupled with the small-amplitude vibrational dynamics. These developments open the route towards simulating rovibrational spectra used to probe methanol in outer space and in precision science laboratories, as well as for probing interactions with external magnetic fields.