Quasiclassical Trajectory Studies of the Photodissociation Dynamics of NO3 from the D0 and D1 Potential Energy Surfaces

We report new global potential energy surfaces (PESs) for the D-0 and D-1 states of NO3. The PESs are permutationally invariant fits to roughly 90 000 electronic energies (MS-CAS(17e,13o)PT2/aug-cc-pVTZ). Hundreds of thousands of quasiclassical trajectories are run from the Do global minimum and one previously identified roaming saddle point as well as a roaming saddle point on D,, identified previously [Xiao, H.; Maeda, S.; Morokuma, K. J. Chem. Theory Comput. 2012, 8, 2600]. The calculations are done at a total energy of relevance to recent experiments where, together with theoretical analysis [Grubb, M. P.; Warter, M. L.; Xiao, H.; Maeda, S.; Morokuma, K; North, S. W. Science 2012, 335, 1075], point to roaming pathways to the O-2+NO products on both D-1 and D-0. Detailed comparisons with experiment are made for the distributions of O-2 vibrational and rotational states, the relative translational energy and the NO rotational states, and the NO v-j vector correlation.