Accurate \textit{ab initio} vibrational energies of methyl chloride

TL;DR

This paper presents highly accurate ab initio potential energy surfaces for methyl chloride, enabling precise vibrational energy calculations that closely match experimental data.

Contribution

The authors developed two new nine-dimensional potential energy surfaces for methyl chloride using high-level ab initio methods, incorporating various corrections for enhanced accuracy.

Findings

Root-mean-square errors of 0.75 and 1.00 cm$^{-1}$ for fundamental vibrational levels.

Both high-level corrections and CBS extrapolation are essential for accurate results.

Achieved vibrational energies are close to experimental values, with limited scope for further refinement without empirical data.

Abstract

Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level \textit{ab initio} theory for the two main isotopologues of methyl chloride, CH$_{3}{}^{35}$Cl and CH$_{3}{}^{37}$Cl. The respective PESs, CBS-35$^{\,\mathrm{HL}}$ and CBS-37$^{\,\mathrm{HL}}$, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY$_3$Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35$^{\,\mathrm{HL}}$ and CBS-37$^{\,\mathrm{HL}}$ PESs reproduce the fundamental term values with root-mean-square errors of $0.75$ and $1.00{\,}$cm$^{-1}$ respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH$_3$Cl without empirical refinement of the respective PESs.