Abstract The role of collisional energy transfer in ion-molecule association reactions is analyzed. Rate constants for the formation of adducts between HCl and NO3-(HNO3)x(H2SO4)y or HSO4-(HNO3)x(H2SO4)y (with x = 0 – 2 and y= 0 – 2) in the buffer gases H2, He, and N2 and at temperatures between 150 and 300 K are considered. Quantum-chemical calculations of molecular parameters and statistical unimolecular rate theory are combined to model low-pressure rate constants whereas ion-molecule capture theory provides high-pressure rate constants. The comparison with experimental results indicates that energy transfer is dominated by overall collision numbers while weak-collision effects are only of minor importance. On the other hand, often neglected falloff effects between termolecular and bimolecular reaction behavior have to be taken into account.

中文翻译：

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He、H2 或 N2 缓冲气体中离子-分子缔合复合物的碰撞稳定性

摘要 分析了碰撞能量转移在离子-分子缔合反应中的作用。在缓冲气体 H2 中，HCl 和 NO3-(HNO3)x(H2SO4)y 或 HSO4-(HNO3)x(H2SO4)y（x = 0 – 2 和 y= 0 – 2）之间形成加合物的速率常数、He 和 N2 以及在 150 到 300 K 之间的温度下被考虑。分子参数的量子化学计算和统计单分子速率理论相结合来模拟低压速率常数，而离子分子捕获理论提供高压速率常数。与实验结果的比较表明，能量转移主要受总碰撞次数的影响，而弱碰撞效应的重要性不大。另一方面，必须考虑到经常被忽视的双分子反应行为和双分子反应行为之间的衰减效应。