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Chemical Selectivity through Control of Excited‐State Dynamics
Author(s) -
Olivucci Massimo,
Santoro Fabrizio
Publication year - 2008
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.200800898
Subject(s) - conformational isomerism , photoexcitation , selectivity , excited state , potential energy surface , wave packet , chemical physics , chemistry , potential energy , throughput , photochemistry , atomic physics , computational chemistry , physics , computer science , molecule , telecommunications , organic chemistry , catalysis , wireless
Trust is good, control is better : In thermal processes in which the interconversion of reactant conformers R 1/2 is faster than the reaction itself, selectivity can be tailored by modulating the energy barriers of competing reaction paths. Ultrafast photoexcitation promotes separate conformers to different regions of the potential energy surface, where the wave packet may reach different conical intersections CI 1/2 , giving rise to product selectivity (P 1/2 ).