Conformational stability of 1-bromo-2-fluoroethane from temperature dependent FT-IR spectra of rare gas solutions

Variable temperature (-55 to -135 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of 1-bromo-2-fluoroethane, BrCH2CH2F, dissolved in liquid krypton and xenon have been recorded. From these data, the enthalpy difference has been determined to be 108 +/- 9 cm(-1) (1.296 +/- 0.113 kJ/mol) and 112 +/- 8 cm(-1) (1.346 +/- 0.098 kJ/mol) from the krypton and xenon solutions, respectively, with the trans conformer the more stable rotamer. Complete vibrational assignments are presented for both conformers which are consistent with the predicted frequencies obtained from the ab initio MP2/6-31G* calculations. The optimized geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, and depolarization ratios have been obtained from RHF/6-31G* and/or MP2/6-31G* ab initio calculations. These quantities are compared to the corresponding experimental quantities when appropriate. Structural parameters and conformational stability have also been obtained from MP2/6-311+G** calculations. Combining the ab initio predicted structural parameters with the microwave rotational constants, ra parameters have been obtained for the gauche conformer. (C) 2000 Published by Elsevier Science B.V. All rights reserved.