Structure and dynamics of radical cations of selectively deuteriated cyclohexanes: an ESR and ab initio study

An ESR study was carried out to elucidate the static and dynamic Jahn–Teller structures of the radical cations of selectively deuteriated cyclohexanes in a cC6F12 matrix, formed by exposure to ionizing radiation at low temperature. Based on the ESR spectra combined with ab initio and density functional theory calculations, the geometrical structure of the radical cations was concluded to be distorted into a C2h symmetry from the original D3d symmetry. The temperature-dependent ESR lineshapes were analyzed in terms of dynamical averaging among the C2h structures with different zero-point vibrational energies due to deuterium mass effects under the assumption of a Boltzmann distribution.