Quantum-chemical ab initio investigation of the vibrational spectrum of halon 1113 and its anharmonic force field: A joint experimental and computational approach

Halon 1113 (chlorotrifluoroethene), used in the synthesis of fluorocarbon-based polymers, has been recently detected in the atmosphere and it is a potential source of chlorine atoms. In this work, the vibrational properties of chlorotrifluoroethene are studied in the 125-5000 cm (1) region by coupling Fourier-transform infrared spectroscopy and high-level ab initio calculations. The vibrational analysis is performed over the whole spectral range and band intensities are obtained in the range 400-3100 cm (1). Ab initio calculations of the anharmonic force field are performed at the coupled cluster level of theory employing either cc-pVTZ or ANO basis sets. Vibration perturbation theory is applied to obtain spectroscopic parameters from the computed anharmonic force fields. The present results provide a solid interpretation of chlorotrifluoroethene vibrational spectrum, and they represent a significant reference for future studies on this molecule, being also the first published data on absorption cross sections and ab initio calculations. (C) 2012 Elsevier B.V. All rights reserved.