Journal of Physical Chemistry A, Vol.119, No.28, 7498-7509, 2015
Nonadiabatic Photodissociation of the Hydroxymethyl Radical from the 2(2)A State. Surface Hopping Simulations Based on a Full Nine-Dimensional Representation of the 1,2,3(2)A Potential Energy Surfaces Coupled by Conical Intersections
The nonadiabatic photodissociation CH2OH(1(2)A) + hv -> CH2OH(2,3(2)A) -> CH2O + H or HCOH(cis or trans) + H is addressed using trajectory surface hopping dynamics on a quasi-diabatic representation, H-d, of the 1,2,3(2)A coupled, adiabatic potential energy surfaces. We focus on dynamics originating on the 2(2)A potential energy surface. The H-d is based exclusively on electronic structure data obtained from a multireference configuration interaction single and double excitation expansion, composed of over 67 million configuration state functions, and treats all nine internal degrees of freedom in an even-handed manner. Each simulation is based on bundles of 10000 trajectories randomly selected from harmonic Wigner distributions and propagated for up to 1 ps. The bimodal distribution in the kinetic energy release spectrum is explained in terms of direct versus quasi-statistical dissociation.