Non-equilibrium phenomena and molecular reaction dynamics: mode space, energy space and conformer space
Non-equilibrium phenomena and molecular reaction dynamics: mode space, energy space and conformer space
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DOI：
10.1080/00268976.2013.780100
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发表时间：
2013-03-01
影响因子：
1.7
通讯作者：
Harvey, Jeremy N.
中科院分区：
文献类型：
--
作者：
Glowacki, David R.;Lightfoot, Robert;Harvey, Jeremy N.
描述和控制远离平衡状态的物质的能力是现代科学面临的前沿挑战。在本文中，我们概述了一种启发式结构，用于思考非平衡现象影响分子反应动力学的不同方式。我们的分析模式包括三种不同的模式，根据不断增加的动态分辨率来组织：在最低分辨率下，我们有共形相空间，在中等分辨率下，我们有能量空间；在最高分辨率下，我们有模式空间。在每个体系中，我们讨论了非平衡现象的实际定义，主要是根据相应的松弛时间尺度。利用这个分析框架，我们讨论了最近的一些非平衡反应动力学研究，包括孤立的小分子体系、气相体系和溶液相体系。这包括新的结果，提供洞察非平衡现象如何影响溶液相烯烃氢硼化反应。我们强调，有趣的非平衡动力学现象经常发生，当松弛时间尺度表征的每个制度是相似的。最后，我们反思了突出的挑战和未来的研究方向，以指导我们对非平衡现象如何影响反应动力学的理解。
The ability to characterise and control matter far away from equilibrium is a frontier challenge facing modern science. In this article, we sketch out a heuristic structure for thinking about the different ways in which non-equilibrium phenomena can impact molecular reaction dynamics. Our analytical schema includes three different regimes, organised according to increasing dynamical resolution: at the lowest resolution, we have conformer phase space, at an intermediate resolution, we have energy space; and at the highest resolution, we have mode space. Within each regime, we discuss practical definitions of non-equilibrium phenomena, mostly in terms of the corresponding relaxation timescales. Using this analytical framework, we discuss some recent non-equilibrium reaction dynamics studies spanning isolated small-molecule ensembles, gas-phase ensembles and solution-phase ensembles. This includes new results that provide insight into how non-equilibrium phenomena impact the solution-phase alkenehydroboration reaction. We emphasise that interesting non-equilibrium dynamical phenomena often occur when the relaxation timescales characterising each regime are similar. In closing, we reflect on outstanding challenges and future research directions to guide our understanding of how non-equilibrium phenomena impact reaction dynamics.