Description:
<jats:p>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 〈ΔE〉 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.</jats:p>