Conformational analysis, structure, and normal coordinate analysis of vibrational spectra of hexafluoroacetone. A density functional theory study

Molecular structure and vibrational spectra of 1,1,1,3,3,3-hexafluoroacetone (HFA) have been investigated by means of ab initio and density functional theory (DFT) calculations. The harmonic and anharmonic vibrational frequencies of HFA were calculated at the B3LYP and B2PLYP levels of theory. The calculated frequencies and the Raman and IR intensities were compared with the experimental results. In addition, a normal coordinate analysis was also done by using the normal mode eigenvectors obtained at the B2PLYP/6-31 + G(d) level. To study the internal rotation of CF 3 groups, single CF 3 rotation and synchronous rotations of both CF 3 groups (clockwise⿿clockwise and clockwise⿿counterclockwise) were analysed. The internal rotation of CF 3 groups around C C bonds in HFA allow four hypothetical conformers (C 2 , C s , and two C 2V point groups). Aided by ab initio and density functional theory (DFT) calculations, the C 2 conformer is the only stable form and the FCCO dihedral angle is in the 17.6⿿21.0° range. Complete vibrational assignments have been reported for the stable C 2 conformer, which is supported by normal coordinate analysis for all fundamentals.