Adamovich I V, Rich J W
Department of Mechanical and Aerospace Engineering, Ohio State University, 201 W. 19th Ave., Columbus, Ohio 43210, USA.
J Chem Phys. 2024 May 21;160(19). doi: 10.1063/5.0209058.
A previously developed semiclassical theory of nonadiabatic energy transfer is used to analyze electronic excitation and quenching in three-dimensional atomic collisions. The predicted transition probabilities, cross sections, and rate coefficients are compared with the quantum scattering calculations for O + O and N + N, for the same interaction potentials and nonadiabatic coupling, and with the experimental data where available. The theory predictions are in very good agreement with quantum scattering, at the conditions when the energy transfer is dominated by a single pair of adiabatic potentials. Closed-form analytic expressions for the cross sections and rate coefficients are obtained, for both the strongly and weakly coupled cases. The results quantify and illustrate the effect of the interaction potentials and their coupling on the energy transfer. The analytic cross sections and rate coefficients are in good agreement with the numerical predictions. The same approach has been used to predict the rate coefficients of electronic excitation and quenching in collisions of N + O atoms. The fidelity of these predictions may be improved considerably if accurate potentials for the excited electronic states of N + O and their coupling are available. The applicability of the semiclassical theory for the prediction of the rates of heavy particle impact excitation in atom-molecule collisions is discussed.
一种先前发展的非绝热能量转移半经典理论被用于分析三维原子碰撞中的电子激发和猝灭。对于相同的相互作用势和非绝热耦合，将预测的跃迁概率、截面和速率系数与O + O和N + N的量子散射计算结果进行比较，并与可获得的实验数据进行比较。在能量转移由一对绝热势主导的条件下，理论预测与量子散射结果非常吻合。对于强耦合和弱耦合情况，都得到了截面和速率系数的封闭形式解析表达式。结果量化并说明了相互作用势及其耦合对能量转移的影响。解析截面和速率系数与数值预测结果吻合良好。同样的方法已被用于预测N + O原子碰撞中电子激发和猝灭的速率系数。如果能获得N + O激发电子态的精确势及其耦合，这些预测的准确性可能会有显著提高。讨论了半经典理论在预测原子 - 分子碰撞中重粒子碰撞激发速率方面的适用性。
