ELECTRONIC-STRUCTURE OF VINYLTHIO RADICAL (CH2CHS) - A THEORETICAL-STUDY

A predictive ab initio MO calculation was performed for the thus far undetected sulfur analog of the vinoxy radical. Multiconfigurational self-consistent field (MCSCF) and symmetry adapted cluster expansion- configuration interaction (SAC-CI) wave functions were used to describe the electronic structure of the radical. The symmetry species of the ground state was found to be 2A ″ as in the case of the vinoxy radical. The crucial difference between the two radicals is that the thio-radical is more or less characterized as a sulfur-centered radical, CH2 = CH-S· whereas the oxy-radical is regarded as a carbon centered CH2-CH = O in their ground state. Excitation energies, normal modes, Franck-Condon factors, hyperfine coupling parameters, and electron affinity were predicted. © 1990 American Institute of Physics.