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The Mechanism for Hydrogen Abstraction by n,π* Excited Singlet States: Evidence for Thermal Activation and Deactivation through a Conical Intersection
Author(s) -
Nau Werner M.,
Greiner Gerhard,
Wall Julia,
Rau Hermann,
Olivucci Massimo,
Robb Michael A.
Publication year - 1998
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/(sici)1521-3773(19980202)37:1/2<98::aid-anie98>3.0.co;2-5
Subject(s) - conical intersection , photochemistry , excited state , hydrogen atom abstraction , kinetic isotope effect , chemistry , deuterium , singlet state , quenching (fluorescence) , singlet oxygen , abstraction , hydrogen , conical surface , mechanism (biology) , molecule , reaction coordinate , computational chemistry , fluorescence , atomic physics , oxygen , physics , materials science , quantum mechanics , organic chemistry , philosophy , epistemology , composite material
A conical intersection along the reaction coordinate of hydrogen abstraction by molecules in n, π * excited singlet states is responsible for the solvent‐induced fluorescence quenching of azoalkanes [see equation]. This novel photochemical reaction mechanism, a case of aborted hydrogen abstraction, was examined by experiment and theory. Mutually consistent results on the observed low activation energies and the deuterium isotope effects were obtained.