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Generalized electronic diabatic approach to structural similarity and the Hammond postulate
Author(s) -
Arteca Gustavo A.,
Tapia O.
Publication year - 2006
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21157
Subject(s) - diabatic , context (archaeology) , quantum , similarity (geometry) , chemistry , electron , complete active space , reaction coordinate , electronic structure , physics , quantum mechanics , computational chemistry , computer science , paleontology , artificial intelligence , atomic orbital , adiabatic process , image (mathematics) , biology
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. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007