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
相关论文
共 48 条
  • [1] [Anonymous], 1994, FEMTOCHEMISTRY
  • [2] Control of chemical reactions by feedback-optimized phase-shaped femtosecond laser pulses
    Assion, A
    Baumert, T
    Bergt, M
    Brixner, T
    Kiefer, B
    Seyfried, V
    Strehle, M
    Gerber, G
    [J]. SCIENCE, 1998, 282 (5390) : 919 - 922
  • [3] Blum K., 1981, Density Matrix Theory and Applications
  • [4] INTRAMOLECULAR DYNAMICS FOR THE ORGANIC CHEMIST
    CARPENTER, BK
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1992, 25 (11) : 520 - 528
  • [5] A highly conformationally specific α- and β-Ala+ decarboxylation pathway
    Choi, Kyo-Won
    Ahn, Doo-Sik
    Lee, Joo-Hee
    Kim, Sang Kyu
    [J]. CHEMICAL COMMUNICATIONS, 2007, (10) : 1041 - 1043
  • [6] Experimental coherent laser control of physicochemical processes
    Dantus, M
    Lozovoy, VV
    [J]. CHEMICAL REVIEWS, 2004, 104 (04) : 1813 - 1859
  • [7] Effects of reagent orbital alignment on product vibrational distributions of the chemiluminescent reaction Ca(P-1(1))+CH3I
    Ding, GW
    Sun, WZ
    Yang, WS
    Xu, DL
    Zhao, RP
    He, GZ
    Lou, NQ
    [J]. CHEMICAL PHYSICS LETTERS, 1997, 265 (3-5) : 392 - 398
  • [8] Domcke W., 2004, Conical Intersections: Electronic Structure, Dynamics and Spectroscopy
  • [9] Advanced Series in Physical Chemistry
  • [10] Some applications of the transition state method to the calculation of reaction velocities, especially in solution.
    Evans, MG
    Polanyi, M
    [J]. TRANSACTIONS OF THE FARADAY SOCIETY, 1935, 31 (01): : 0875 - 0893
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