Chemical selectivity through control of excited-state dynamics

被引：35
|
作者：
Olivucci, Massimo [1 ,2 ]
Santoro, Fabrizio [3 ]
机构：
[1] Univ Siena, Dipartimento Chim, I-53100 Siena, Italy
[2] Bowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
[3] Ist & Proc Chim Fis, CNR, Area Ric, I-56124 Pisa, Italy
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 34期
关键词：
conformation selectivity; conical intersections; orbital alignment; reaction mechanisms; stereodynamics;
D O I：
10.1002/anie.200800898
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Graph Presented) Trust is good, control is better: In thermal processes in which the interconversion of reactant conformers R1/2 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 CI1/2, giving rise to product selectivity (P1/2). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码：6322 / 6325
页数：4
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