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Modelling Photochemical Reactivity of Organic Systems — A New Challenge to Quantum Computational Chemistry
Author(s) -
Bernardi Fernando,
Olivucci Massimo,
Robb Michael
Publication year - 1993
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199300033
Subject(s) - chemistry , conical intersection , quantum yield , quantum chemistry , quantum , rationalization (economics) , computational chemistry , yield (engineering) , reactivity (psychology) , chemical physics , fluorescence , molecule , organic chemistry , quantum mechanics , supramolecular chemistry , thermodynamics , medicine , philosophy , physics , alternative medicine , epistemology , pathology
The applicability of modern methods of quantum computational chemistry to the problem of modelling photochemical mechanisms is discussed. It is demonstrated that one of the central mechanistic features is the surface‐crossing region which takes the form of a conical intersection. It is shown that this mechanistic feature can yield a new rationalization of common experimental observations such as the simultaneous production of different photoproducts, the occurrence of rigid stereochemistry, and the occurrence of very low fluorescence quantum yields. In addition, a simple VB model can often lead to accurate predictions about the nature of the surface‐crossing region and the nature of the recoupling pathways on the ground‐state surface.