Premium
A Tiny Excited‐State Barrier Can Induce a Multiexponential Decay of the Retinal Chromophore: A Quantum Dynamics Investigation
Author(s) -
Olivucci Massimo,
Lami Alessandro,
Santoro Fabrizio
Publication year - 2005
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/anie.200501236
Subject(s) - conical intersection , excited state , chromophore , quantum , retinal , wave packet , quantum zeno effect , chemistry , ridge , physics , molecular physics , chemical physics , atomic physics , quantum mechanics , photochemistry , quantum dissipation , biochemistry , paleontology , biology
Excitement over something small : The protonated Schiff base of retinal photoisomerizes on an excited‐state hypersurface (S 1 ) that connects the Franck–Condon (FC) point via a flat valley centered on a planar structure (SP) to a conical intersection (CI; see picture). Wave‐packet (gray hat) quantum dynamics shows that the depletion of the S 1 population switches from mono‐ to biexponential when a small ridge (dotted line) between SP and CI is present.