Generalized electronic diabatic approach to structural similarity and the Hammond postulate
Generalized electronic diabatic approach to structural similarity and the Hammond postulate
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DOI：
10.1002/qua.21157
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发表时间：
2007-02-01
影响因子：
2.2
通讯作者：
Tapia, O.
中科院分区：
文献类型：
--
作者：
Arteca, Gustavo A.;Tapia, O.
我们重新审视的概念结构相似性沿着反应路径的范围内的广义电子非绝热（GED）分子模型。在这种方法中，涉及两个闭壳层稳定物种的反应被描述为叠加至少三个非绝热电子物种（反应物，产物和开壳层过渡态）通过外部电磁场耦合的量子态的演化。反应物和产品的振幅在这个一般的状态也调制通过改变与电子相互作用的经典正电荷系统的几何形状。通过将这些振幅映射到核构型空间，我们可以沿着反应坐标沿着跟踪总量子态，并建立它与每个非绝热物质的相似性。结果，化学过程和一些有用的概念，如能垒和哈蒙德假设，都是量子态之间类似弗兰克-康登跃迁的结果。(c)2006 Wiley Periodicals，Inc.
We revisit the notion of structural similarity along a reaction path within the context of a generalized electronic diabatic (GED) molecular model. In this approach, a reaction involving two closed-shell stable species is described as the evolution of a quantum state that superimposes at least three diabatic electronic species (reactant, product, and an open-shell transition state) coupled by an external electromagnetic field. Reactant and product amplitudes in this general state are also modulated by changing the geometry of a system of classical positive charges interacting with the electrons. By mapping these amplitudes over nuclear configurational space, we can follow the total quantum state along a reaction coordinate and establish its similarity to each of the diabatic species. As a result, chemical processes, and useful notions such as those of energy barriers and the Hammond postulate, emerge as consequence of Franck-Condon-like transitions between quantum states. (c) 2006 Wiley Periodicals, Inc.