Green William H
Massachusetts Institute of Technology, 77 Massachusetts Ave. E17-504, Cambridge, MA 02139, USA.
Faraday Discuss. 2022 Oct 21;238(0):741-766. doi: 10.1039/d2fd00136e.
This , marking the centenary of Lindemann's explanation of the pressure-dependence of unimolecular reactions, presented recent advances in measuring and computing collisional energy transfer efficiencies, microcanonical rate coefficients, and pressure-dependent (phenomenological) rate coefficients, and the incorporation of these rate coefficients in kinetic models. Several of the presentations featured systems where breakdown of the Born-Oppenheimer approximation is key to understanding the measured rates/products. Many of the reaction systems presented were quite complex, which can make it difficult to go from "plausible proposed explanation" to "quantitative agreement between model and experiment". This complexity highlights the need for better automation of the calculations, better documentation and benchmarking to catch any errors and to make the calculations more easily reproducible, and continued (and even closer) cooperation of experimentalists and modelers. In some situations the correct definition of a "species" is debatable, since the population distributions and time evolution are so distorted from the perfect-Boltzmann Lewis-structure zero-order concept of a chemical species. Despite all these challenges, the field has made tremendous advances, and several cases were presented which demonstrated both excellent understanding of very complicated reaction chemistry and quantitatively accurate predictions of complicated experiments. Some of the interesting contributions to this are highlighted here, with some comments and suggestions for next steps.
这是为纪念林德曼对单分子反应压力依赖性的解释一百周年而举办的活动,展示了测量和计算碰撞能量转移效率、微正则速率系数以及压力依赖性(唯象)速率系数方面的最新进展,以及将这些速率系数纳入动力学模型的情况。其中一些报告介绍了以玻恩 - 奥本海默近似失效为理解测量速率/产物关键的系统。所展示的许多反应系统相当复杂,这使得从“合理的推测性解释”到“模型与实验之间的定量一致”变得困难。这种复杂性凸显了对计算进行更好自动化的必要性,需要更好的文档记录和基准测试以发现任何错误并使计算更易于重现,以及实验人员和建模人员持续(甚至更紧密)合作的必要性。在某些情况下,“物种”的正确定义存在争议,因为种群分布和时间演化与化学物种的完美玻尔兹曼 - 刘易斯结构零阶概念相差甚远。尽管存在所有这些挑战,该领域仍取得了巨大进展,并且展示了几个案例,这些案例既体现了对非常复杂反应化学的出色理解,又对复杂实验进行了定量准确的预测。这里突出了其中一些有趣的贡献,并对下一步提出了一些评论和建议。