Dynamics of the O + CN reaction and N + CO scattering on two coupled surfaces

Abstract

Spin-orbit coupling between the two collinear (2)Pi and (4)Sigma(-) potential energy surfaces for the NCO system are calculated using the RASSI method with CASSCF wave functions as basis set. The GDVR method has been used to interpolate a spin-orbit coupling surface. Wave packet and quasi-classical trajectory surface hopping calculations have been performed and compared for both the O((3)P) + CN(X(2)Sigma(+)) --> N((4)S) + CO(X(1)Sigma(+)) reaction and for electronically inelastic scattering in the N + CO channels. The O + CN nonadiabatic reaction probabilities are small. The wavepacket study gives a resonance structure. Also for the N + CO electronically inelastic scattering the wave packet calculations give a distinct resonance structure with peak transition probabilities up to around 10%, which is somewhat lower than the trajectory surface hopping results.