Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

Abstract

We present a theoretical investigation of oxalyl fluoride (COF) 2 in the ground and the four lowest excited (two singlet and two triplet) electronic states of the n,π∗-type mainly with the CASPT2(8-6)/cc-pVTZ method. Geometries, vibrational frequencies, potential energy functions of internal rotation, and adiabatic electronic transition energies were obtained. The conformer energy difference and the barrier to internal rotation in the ground electronic state were extrapolated to the complete basis set limit. The planar trans and cis conformations were the most stable configurations for all five electronic states under study. We found that the allowed electronic transition of the cis conformer has a transition energy that is significantly higher than that predicted in previous studies. For the excited states, the internal rotation was found to be accompanied by significant non-planar distortion of both carbonyl fragments, indicating strong coupling between these molecular motions.