Issue 43, 2019

Mode-specific quantum dynamics and kinetics of the hydrogen abstraction reaction OH + H2O → H2O + OH

Abstract

Hydrogen abstraction processes are prevalent in a wide range of chemically active environments. In this work, the prototypical hydrogen exchange reaction OH + H2O → H2O + OH is investigated on an accurate ab initio based potential energy surface using an initial state-selected time-dependent wave packet method. Exciting either the symmetric stretching mode or the antisymmetric stretching mode of the reactant H2O promotes the reaction more than exciting the bending mode. The vibrational energy initially deposited in H2O is more efficient than the translational energy in promoting the reaction. There exists a remarkable synergistic effect between the stretching mode and the bending mode as the efficacy for the combination band excitation is larger than the sum of individual excitations. The mode-specific dynamics is partially rationalized by the sudden vector projection model. Besides, the mode-specific rate constants apparently exhibit a strong non-Arrhenius behavior at low and moderate temperatures.

Graphical abstract: Mode-specific quantum dynamics and kinetics of the hydrogen abstraction reaction OH + H2O → H2O + OH

Article information

Article type
Paper
Submitted
26 Aug 2019
Accepted
09 Oct 2019
First published
10 Oct 2019

Phys. Chem. Chem. Phys., 2019,21, 24054-24060

Mode-specific quantum dynamics and kinetics of the hydrogen abstraction reaction OH + H2O → H2O + OH

R. Zheng, Y. Zhu and H. Song, Phys. Chem. Chem. Phys., 2019, 21, 24054 DOI: 10.1039/C9CP04721B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements