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Intrinsically Competitive Photoinduced Polycyclization and Double‐Bond Shift through a Boatlike Conical Intersection
Author(s) -
Garavelli Marco,
Bernardi Fernando,
Moliner Vicente,
Olivucci Massimo
Publication year - 2001
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/1521-3773(20010417)40:8<1466::aid-anie1466>3.0.co;2-r
Subject(s) - conical intersection , conical surface , intersection (aeronautics) , double bond , gas phase , ab initio , ab initio quantum chemistry methods , chemistry , computational chemistry , chemical physics , materials science , molecule , organic chemistry , engineering , composite material , aerospace engineering
A mechanistic view of the deactivation of photoexcited cycloocta‐1,3,5,7‐tetraene (COT*) through a novel type of conical intersection (see scheme) is provided by ab initio studies. As a consequence of this deactivation, the formation of semibullvalene (SBV) and of the double‐bond‐shifted isomer of COT are intrinsically bound. Both gas‐phase and solution‐phase experimental data are explained.