Generalized electronic diabatic approach to structural similarity and the Hammond postulate
2007 (Swedish)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 107, no 2, 382-395 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2007. Vol. 107, no 2, 382-395 p.
diabatic states, energy barriers, transition state, Hammond postulate, reaction probabilities
IdentifiersURN: urn:nbn:se:uu:diva-24304DOI: 10.1002/qua.21157ISI: 000242652700018OAI: oai:DiVA.org:uu-24304DiVA: diva2:52078