A Combined Empirical-ab initio Determination of the General Harmonic Force Field of Ketene.

Abstract The general harmonic force field (GHFF) of ketene has been determined through a joint empirical-ab initio investigation. Perturbations in the infrared spectra of all isotopic species render experimental frequency data of limited discriminatory value in the empirical determination. Microwave/infrared determined quartic distortion constants are found to be mutually incompatible, both within and between isotopic species. The sensitivity of the distortion constants to truncation and constraints made in their determination is established in order to make a realistic estimate of their reliability in the force constant calculations. Ab initio calculations performed at various different levels of sophistication predict consistent values for interaction constants, some of which are markedly different from previously reported empirical values. The joint empirical-ab initio GHFF reproduces all observed and perturbation-corrected data well over five isotopic species. Coriolis interaction constants are calculated for ketene-H 2 , -HD, and -D 2 , which will be of assistance to future analyses, particularly of the strongly interacting four-level systems below 1000 cm −1 . Scaled ab initio force constants, calculated around the experimental ground state geometry as reference, are in excellent agreement with the empirical values, with one exception, which arises due to neglect of configuration interaction.