Journal of Chemical Physics, Vol.116, No.16, 7040-7048, 2002
Statistical model of energy transfer in molecular collisions: De-energization of highly excited toluene
Recent experimental data on the collisional de-energization of toluene from initial energies of between 10 000 and 49 000 cm(-1) have been analyzed by the partially ergodic collision theory. The data for 11 different gases were obtained by kinetically controlled selective ionization by Luther and co-workers [J. Chem. Phys. 112, 4076 (2000)] and are of exceptional detail and reliability. The semiempirical PECT model starts from the average energy transferred per collision [DeltaE] and predicts the full transition probability P(E',E) to good accuracy. The energy transfer efficiency is about a tenth of the ergodic collision limit with only minor dependence on gas molecule or initial toluene energy.