High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

Abstract

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm −1. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν 4 (1200.7341 cm −1) and ν 13 (1223.3 cm −1) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν 4 ( J max = 86, K a max = 50) and 2921 lines to ν 13 ( J max = 60, K a max = 54). Effective rotational and centrifugal distortion constants were determined for ν 4, and the polarization ratio was found to be Δ μ a 2 / Δ μ c 2 = 1.0 : 1.1 . Severe Coriolis perturbations prevent any satisfactory fit to the ν 13 band.