Ab initio MO studies on the photodissociation of the methoxy family CX(3)Y (X=H,F; Y=O,S) from the (A)over-tilda(2)A(1) state

Ab initio MO calculations have been carried out for the photodissociation of the methoxy radical family CX(3)Y (X = H, F, Y = O, S) from the (A) over tilde(2)A(1) state. Three channels are considered. (i) predissociation to CX(3) + Y, (2) isomerization to CX(2)-YX followed by dissociation to CX(2) + YX, and (3) dissociation of X giving CX(2)Y + X. Minima on the seam of crossing (MSXs) between the bound (2)A(1) state and (2)A(2), (4)A(2) and (4)E repulsive states as well as transition states on each surface are located. The branching to the three channels is discussed based on the energetics of these critical points, Final internal energy distribution is briefly discussed based on the meta-intrinsic reaction coordinate.