Trajectory simulations for unimolecular dissociations with application to the dissociation of NCNO

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Abstract
A classical trajectory‐based procedure for estimating the kinetics of unimolecular dissociations containing no reverse potential barrier is described and implemented for the dissociation of NCNO into NC and NO. The basis of this implementation involves Keck’s procedure of propagating trajectories from the transition state on towards separated fragments and back towards complex. A separation of modes into the ‘‘transitional’’ and ‘‘conserved’’ modes allows for a propagation in only the transitional modes via the implementation of adiabaticity assumptions for the conserved modes. A statistical distribution of initial conditions is obtained via the implementation of Monte Carlo based procedures previously employed in the evaluation of the number of available states. The trajectory results for the rate constants and the product rotational distributions are compared with corresponding statistical results. A recently introduced variable reaction coordinate statistical approach is found to provide an accurate estimate to the rate constants when the effects of two separate transition states are incorporated. Meanwhile, as expected, the product rotational distributions deviate only slightly from phase space theory predictions.

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