Collisional energy transfer: general discussion
Collisional energy transfer: general discussion
复制标题
碰撞能量转移：一般讨论
DOI：
10.1039/d2fd90048c
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发表时间：
2022
影响因子：
3.4
通讯作者：
Jasper, Ahren W.
中科院分区：
文献类型：
--
作者：
Babikov, Dmitri;Burke, Michael P.;Casavecchia, Piergiorgio;Green, William H.;Grinberg Dana, Alon;Guo, Hua;Heard, Dwayne E.;Heathcote, David;Hochlaf, Majdi;Jasper, Ahren W.
Robin J. Shannon在Stephen J. Klippenstein的介绍性演讲开始讨论：我对你成功地使用统计方法来处理漫游激进通道感到惊讶和鼓舞。你能进一步评论一下为什么统计速率理论似乎能预测这种动力学过程的原因吗？斯蒂芬·J·克利彭斯坦回答说：人们确实期待一些动力学效应，特别是在通过内部过渡态时继续解离的倾向。我认为我的研究结果表明，这些偏见并不像人们想象的那么大。总的来说，仍然有一个潜在的，或多或少的统计，采样的取向运动。值得注意的是，对于更复杂的情况，例如由Criegee中间体产生的乙烯基氢过氧化物的RO/OH分解，货车德瓦尔斯络合物体系中相互作用强度的增加将导致运动的甚至更有效的随机化。
Robin J. Shannon opened discussion of the introductory lecture by Stephen J. Klippenstein: I was surprised and heartened by your success in using a statistical approach to treat roaming radical channels. Could you comment further on the reasons why statistical rate theory appears to be predictive for such dynamical processes?Stephen J. Klippenstein answered: One does expect some dynamical effects, particularly with biases toward continuing to dissociate a er passing the inner transition state. I think what my results indicate is that those biases are not as large as one might think. Overall, there is still an underlying, more or less statistical, sampling of the orientational motions. Notably, for more complex cases, such as the RO/OH ssions of the vinyl hydroperoxides arising from Criegee intermediates, the increased strength of the interactions in the van der Waals complex regime will lead to even more effective randomization of the motions.