Issue 7, 2016

Control of chemical reactivity by transition-state and beyond


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. 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.

Graphical abstract: Control of chemical reactivity by transition-state and beyond

Article information

Article type
08 Mar 2016
06 Apr 2016
First published
13 Apr 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 3992-4003

Control of chemical reactivity by transition-state and beyond

H. Guo and K. Liu, Chem. Sci., 2016, 7, 3992 DOI: 10.1039/C6SC01066K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity