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Title: Control of chemical reactivity by transition-state and beyond

Abstract

It has been long established that the transition state for an activated reaction controls the overall reactivity, serving as the bottleneck for reaction flux. However, the role of the transition state in regulating quantum state resolved reactivity has only been addressed more recently, thanks to advances in both experimental and theoretical techniques. Here in this perspective, we discuss some recent advances in understanding mode-specific reaction dynamics in bimolecular reactions, mainly focusing on the X + H 2O/CH 4 (X = H, F, Cl, and O( 3P)) systems, extensively studied in our groups. These advances shed valuable light on the importance of the transition state in mode-specific and steric dynamics of these prototypical reactions. It is shown that many mode-specific phenomena can be understood in terms of a transition-state based model, which assumes in the sudden limit that the ability of a reactant mode for promoting the reaction stems from its coupling with the reaction coordinate at the transition state. Yet, in some cases the long-range anisotropic interactions in the entrance (or exit) valley, which govern how the trajectories reach (or leave) the transition state, also come into play, thus modifying the reactive outcomes.

Authors:
ORCiD logo [1];  [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
  2. Academia Sinica, Taipei (Taiwan). Inst. of Atomic and Molecular Sciences; National Taiwan Univ., Taipei (Taiwan). Dept. of Physics
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1467451
Grant/Contract Number:  
FG02-05ER15694
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Guo, Hua, and Liu, Kopin. Control of chemical reactivity by transition-state and beyond. United States: N. p., 2016. Web. doi:10.1039/c6sc01066k.
Guo, Hua, & Liu, Kopin. Control of chemical reactivity by transition-state and beyond. United States. doi:10.1039/c6sc01066k.
Guo, Hua, and Liu, Kopin. Wed . "Control of chemical reactivity by transition-state and beyond". United States. doi:10.1039/c6sc01066k. https://www.osti.gov/servlets/purl/1467451.
@article{osti_1467451,
title = {Control of chemical reactivity by transition-state and beyond},
author = {Guo, Hua and Liu, Kopin},
abstractNote = {It has been long established that the transition state for an activated reaction controls the overall reactivity, serving as the bottleneck for reaction flux. However, the role of the transition state in regulating quantum state resolved reactivity has only been addressed more recently, thanks to advances in both experimental and theoretical techniques. Here in this perspective, we discuss some recent advances in understanding mode-specific reaction dynamics in bimolecular reactions, mainly focusing on the X + H2O/CH4 (X = H, F, Cl, and O(3P)) systems, extensively studied in our groups. These advances shed valuable light on the importance of the transition state in mode-specific and steric dynamics of these prototypical reactions. It is shown that many mode-specific phenomena can be understood in terms of a transition-state based model, which assumes in the sudden limit that the ability of a reactant mode for promoting the reaction stems from its coupling with the reaction coordinate at the transition state. Yet, in some cases the long-range anisotropic interactions in the entrance (or exit) valley, which govern how the trajectories reach (or leave) the transition state, also come into play, thus modifying the reactive outcomes.},
doi = {10.1039/c6sc01066k},
journal = {Chemical Science},
number = 7,
volume = 7,
place = {United States},
year = {Wed Apr 13 00:00:00 EDT 2016},
month = {Wed Apr 13 00:00:00 EDT 2016}
}

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Cited by: 26 works
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Works referenced in this record:

Click Chemistry: Diverse Chemical Function from a Few Good Reactions
journal, June 2001


Laser Control of Chemical Reactions
journal, March 1998