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THE ROLE OF BIRADICALOID GEOMETRIES IN ORGANIC PHOTOCHEMISTRY
Author(s) -
Michl Josef
Publication year - 1977
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1977.tb07436.x
Subject(s) - chemistry , excited state , photochemistry , atomic orbital , ground state , chemiluminescence , adiabatic process , molecule , computational chemistry , molecular orbital , simple (philosophy) , electron , atomic physics , physics , organic chemistry , philosophy , quantum mechanics , epistemology , thermodynamics
— Excited molecules tend to return to the ground state at biradicaloid geometries, i.e. those for which the simple MO description yields two non‐bonding orbitals occupied by only two electrons in the ground state. The nature of electronic states at these geometries and the consequences for the course of photochemical reactions are summarized, using the cases of H 2 and H 4 as simple models. Several aspects of classification schemes for photochemical reactions are discussed. Detailed mechanisms of photocycloaddition, of adiabatic photochemical rearrangement of Dewar aromatics, and of luminol chemiluminescence are considered as examples.