Journal of Chemical Physics, Vol.116, No.19, 8300-8306, 2002
Photodissociation of the hydroxymethyl radical. I. The role of conical intersections in line broadening and decomposition pathways
When the 3 (2)A state of D2COH is excited broadened lines are observed and both D and H atoms are produced. When the 2 (2)A state is excited the spectrum is quite diffuse. These experimental observations can be explained by conical intersections connecting the 3 (2)A and 2 (2)A states and the 2 (2)A and 1 (2)A states. The 2 (2)A<--1 (2)A excitation leads to rapid dissociation as a result of a seam of conical intersections connecting the 2 (2)A and 1 (2)A states. The relevant region of the 2 (2)A-1 (2)A seam of conical intersections occurs for long R(O-H) and can lead to ground state D2CO+H. Following the 3 (2)A<--1 (2)A excitation a low energy portion of the 2 (2)A-3 (2)A seam of conical intersection can be accessed. This portion of the 2 (2)A-3 (2)A seam occurs for long R(D-C). From this seam of conical intersections, paths on the 2 (2)A potential energy surface lead to portions of the 2 (2)A-1 (2)A seam from which either of the ground state dissociation products DCOH+D, or D2CO+H are accessible.