Corrections to Vibrational Transition Probabilities Calculated from a Three-Dimensional Model

Abstract

Corrections to the collision-induced vibration transition probability calculated by Hansen and Pearson from a three-dimensional semiclassical model are examined. These corrections come from the retention of higher order terms in the expansion of the interaction potential and the use of the actual value of the deflection angle in the calculation of the transition probability. It is found that the contribution to the transition cross section from previously neglected potential terms can be significant for short range potentials and for the large relative collision velocities encountered at high temperatures. The correction to the transition cross section obtained from the use of actual deflection angles will not be appreciable unless the change in the rotational quantum number is large.