Quantum and Semiclassical Dynamics of Nonadiabatic Electronic Excitation of C(3P) to C1D) by Hyperthermal Collisions with N2.

Abstract

The dynamics and kinetics of nonadiabatic excitation of C(3P) to C(1D) induced by hyperthermal collisions with N2 molecules are investigated using a quantum mechanical and two semiclassical nonadiabatic methods. The full-dimensional interaction potential energy surfaces and spin-orbit coupling, which facilitates the spin-forbidden process, are represented by a recently constructed diabatic potential energy matrix. The multistate quantum dynamics for selected partial waves found small transition probabilities due to the weak spin-orbit coupling. The spin-flip transition is the most favored near the threshold due to effective curve crossing. Strong oscillations are also found in the probabilities, which are attributable to resonances supported by the deep well in the singlet-state potential. Vibrational state-specified rate coefficients are reported from J-shifted quantum dynamics calculations, and they follow the Arrhenius form. Vibrational excitation in the N2 collision partner is found to increase the excitation rate at low temperatures, but the trend is reversed at high temperatures. The two semiclassical methods qualitatively reproduce the quantum rate coefficients.