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American Chemical Society, Journal of the American Chemical Society, 9(125), p. 2804-2808, 2003

DOI: 10.1021/ja027352l

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Relationship between Photoisomerization Path and Intersection Space in a Retinal Chromophore Model

Journal article published in 2003 by Annapaola Migani, Michael A. Robb, Massimo Olivucci ORCID
This paper is available in a repository.
This paper is available in a repository.

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Data provided by SHERPA/RoMEO

Abstract

A low-lying segment of the intersection space (IS) between the excited-state and the ground-state energy surfaces of a retinal chromophore model has been mapped using ab initio CASSCF computations. Analysis of the structural relationship between the computed IS cross-section and the excited state Z --> E isomerization path shows that these are remarkably close both in energy and in structure. Indeed, the IS segment and the Z --> E path remain roughly parallel and merge only when the double bond reaches a 70 degree twisting. This finding supports the idea that, in certain chromophores, a more extended segment of IS, and not a single conical intersection, contributes to the decay to the ground state.