AN AB-INITIO CALCULATION OF THE ROTATION AND INTERNAL-ROTATION ENERGY-LEVELS OF THE ETHYL RADICAL

By ab initio calculation at ten values of the internal-rotation angle we have determined the minimum energy path for internal-rotation in th e ethyl radical C2H5. Bond-length and bond-angle relaxation are allowe d via full optimization, using unrestricted second-order Moller-Plesse t perturbation theory, for each choice of torsional dihedral angle. We find that the only significant relaxation is a wagging (or inversion) of the CH2 group through +/- 9 degrees about a planar C-CH2 geometry as the internal-rotation proceeds. The torsional potential can be accu rately fitted to a V-6 function and the barrier to internal-rotation i s calculated to be 26 cm(-1). Using our general rotation-contortion Ha miltonian and computer program we have calculated the rotation-torsion energy levels of the molecule using this minimum-energy path. Brief c omparison is made to recent experimental measurements of the rotationa l fine structure of the v(9) = 1 fundamental. (C) 1998 Elsevier Scienc e B.V.