Infrared and Raman spectra, ab initio calculations and vibrational assignment for 3-fluoro-1-butyne

Abstract

The infrared (3500-80 cm −1) and Raman (3500-20 cm −1) spectra of 3-fluoro-1-butyne, CH 3CHFCCH, have been recorded for the gas and solid. Additionally, the Raman spectrum of the liquid has also been recorded to aid in the vibrational assignment. Ab initio electronic structure calculations of energies, geometrical structures, vibrational frequencies, infrared intensities, Raman activities and the potential energy function for the methyl torsion have been calculated to assist in the interpretation of the spectra. The fundamental torsional mode is observed at 251 cm −1 with a series of sequence peaks falling to lower frequency. The three-fold methyl torsional barrier is calculated to be 1441 ± 20 cm −1 (4.12 ± 0.06 kcal mol −1) where the uncertainty is partly due to the uncertainty in values of the V 6 term. A complete vibrational assignment is proposed based on band contours, relative intensities, and ab initio predicted frequencies. Several fundamentals are significantly shifted in the condensed phases compared to values in the vapor state.