Exact quantum dynamics of methanol: Full-dimensional <i>ab initio</i> potential energy surface of spectroscopic quality and variational vibrational states

Abstract

The methanol molecule is a sensitive probe of astrochemistry, astrophysics, and fundamental physics. The first-principles elucidation and prediction of its rotational–torsional–vibrational motions are enabled in this work by the computation of a full-dimensional, 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 tunneling splittings are computed up to the first overtone of the C–O stretching mode by direct numerical solution of the vibrational Schrödinger 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 tunneling splittings coupled with the small-amplitude vibrational dynamics. These developments open the route toward 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.