A New Look at the Transition State: Wigner's Dynamical Perspective Revisited
A New Look at the Transition State: Wigner's Dynamical Perspective Revisited
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对过渡状态的新看法：重新审视维格纳的动力学观点
DOI：
10.1002/0471712531.ch3
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
T. Uzer
中科院分区：
文献类型：
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作者：
C. Jaffé;Shinnosuke Kawai;J. Palacián;P. Yanguas;T. Uzer
过渡态的概念是化学中的一个统一概念。许多化学反应理论明确地假设，一旦反应物通过过渡态，它们就不能返回。这个不重交叉规则用来定义过渡态，是过渡态理论的核心。尽管它在化学中无处不在，但直到最近才证明了两个以上自由度的过渡态的存在。目前还没有一个普遍的理论可以用来真正找到过渡态。在这里，结合天体力学的方法与动力系统理论的最新进展，我们提供了一个理论，是严格有效的任意数量的自由度。同样重要的是，计算能力的进步使该方法在实践中适用于大型系统。过渡态是一种相空间对象，了解它使我们能够精确地区分反应性和非反应性分子构型，无论它们位于相空间的何处。
The notion of a transition state is one of the grand unifying concepts in chemistry. Many theories of chemical reactions explicitly assume that once reactants pass through the transition state then they cannot return. This no-recrossing rule serves to define the transition state and is central to transition state theory. Despite its ubiquity in chemistry it is only recently that the existence of the transition state in more than two degrees-of-freedom has been proven. No general theory has existed for actually finding the transition state. Here, combining methods of celestial mechanics with recent advances in dynamical systems theory, we provide a theory that is rigorously valid for an arbitrary number of degrees-of-freedom. Equally important, advances in computational power make the method applicable in practice for large systems. Knowledge of the transition state, a phase space object, allows us to differentiate, with exquisite precision, between reactive and nonreactive molecular configurations wherever they lie in phase space.
Y.Aoki.：Theochem。
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