A highly accurate {\it ab initio} potential energy surface for methane

TL;DR

This paper presents a highly accurate nine-dimensional ab initio potential energy surface for methane, achieved through advanced quantum chemistry calculations, enabling precise vibrational energy level predictions and serving as a foundation for further refinement.

Contribution

The authors developed the most accurate ab initio methane PES to date using state-of-the-art methods, incorporating extensive corrections for high precision.

Findings

Achieved sub-wavenumber accuracy for vibrational levels

Reproduced fundamental vibrational frequencies with 0.70 cm$^{-1}$ RMS error

Provided a reliable starting point for empirical PES refinement

Abstract

A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art \textit{ab initio} theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include: core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of $^{12}$CH$_4$ reproduced with a root-mean-square error of $0.70{\,}$cm$^{-1}$. The computed \textit{ab initio} equilibrium C{--}H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as $J$ (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate \textit{ab initio} surface to date and will serve as a good starting point for empirical refinement.