Conformational properties, torsional potential, and vibrational force field for methacryloyl fluoride - An ab initio investigation

The structure, torsional potentials, vibrational spectra, and harmonic force fields for s-cis and s-trans isomers of methacryloyl fluoride are examined to understand the conformational properties of the molecules and their relationship to macroscopic polymer properties. The structure is found to be in good agreement with experiment. It is shown by calculations that the energy difference between the cis and the transisomers is less than 1 kcal/mol at both the split valence and the split valence polarized levels, with the trans form favored. Analysis of the torsional potentials indicates that a rigid rotor model provides a reasonable description of the motion of the COF group in the molecule. The torsional barrier to interconvert the s-trans to the s-cis form is found to be 7.0 kcal/mol. A fit of the data to a three-term Fourier series shows that it is possible to reproduce the experimentally derived barrier, even though a direct determination indicates that the barrier is higher.