The CH + N₂ association reaction at low temperatures: Ab initio MO/VRRKM-theory analysis of temperature and pressure effects

The microcanonical variational RRKM formalism combined with high level ab initio and density functional calculations has been applied to the reaction of CH(²π) with molecular nitrogen at low and moderate temperatures. The existing experimental T, P-dependent data for T< 1000 K could be theoretically accounted for. Our simulations reproduced very well the strong negative temperature and strong positive pressure effects observed experimentally. The comparison with less rigorous variational techniques demonstrates the importance of the microscopic rate constant minimization at the E and J resolved level.