The methylene saga continues: Stretching fundamentals and zero-point energy of [formula omitted] CH 2

Abstract

The vibrational fundamentals and the rotational levels up to J=7 of the X ˜ 3 B 1 and a ˜ 1 A 1 electronic states of CH 2 have been computed completely ab initio. The calculations were based on converged, variational nuclear motion calculations employing high-quality ab initio quartic force field approximations of the related potential energy surfaces (PES). The vibrational fundamentals obtained are compared to other computational results, namely those obtained from second-order vibrational perturbation theory (VPT2) and the nonrigid-rotation-large-amplitude-internal-motion Hamiltonian (NRLH) approach. The variationally computed rotational transitions are compared both to experimentally available results and to results obtained using empirical, fitted PESs. The comparisons suggest that while the fitted PESs of X ˜ 3 B 1 CH 2 reproduce excellently the available rovibrational transition wavenumbers, the corresponding stretching fundamental term values, which have not been determined experimentally, are less accurate than the ab initio values obtained in the present study. This means that the zero-point energy (ZPE) computed ab initio in the present work is an improvement over that computed from the fitted PES of X ˜ 3 B 1 CH 2. No similar problems are observed for the semirigid a ˜ 1 A 1 state of CH 2, where the computed, the fitted, and the experimental results all agree with each other. The symmetric and antisymmetric stretching fundamentals of X ˜ 3 B 1 CH 2 obtained in this study are 3035±7 and 3249±7 cm −1, respectively. The corresponding ZPE of X ˜ 3 B 1 is 3733±10 cm −1, while that of a ˜ 1 A 1 CH 2 is 3605±15 cm −1.