STUDY OF ELECTRONIC STRUCTURE OF RADICALS BY CI METHOD .3. EXCITED STATES OF BENZYL RADICAL

There are presented the results in the π-electronic approximation for some properties of the excited doublet states of the benzyl radical obtained by the CI method on the SCF closed and open shell orbitals taking into account all singly and some doubly excited configurations. Also the first quartet and sextet states were computed by the SCF open shell theory in the one-configurational approximation. The energies and transition moments agree well with the available experimental data. The classification and the assignment of the excited terms are given. The calculated spectrum is strongly distorted when the set of all singly excited configurations is truncated. The inclusion of the doubly excited configurations leads also to a significant distortion of the spectrum changing the mutual order of the neighbouring terms in some cases. The transition from the closed shell orbitals to the open shell ones results in a considerable lowering of all terms. As in the case of the triplet molecular terms the decrease of the electronic interaction brings together the lowest excited term of the radical with its ground state term. The electronic and spin density distributions in the excited states of the benzyl radical are computed. © 1969 Springer-Verlag.