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Tunneling in Unimolecular and Bimolecular Reactions

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Book cover Molecular Quantum Dynamics

Part of the book series: Physical Chemistry in Action ((PCIA))

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Abstract

Tunneling is an important quantum phenomenon in reaction dynamics. In this chapter, the effects of tunneling on photodissociation and reactive scattering are discussed using two prototypical examples. The first deals with a unimolecular decomposition reaction, namely the photodissociation of NH3 in its first (A) absorption band and the second is concerned with an important bimolecular reaction in combustion: HO + CO → H + CO2. In the former case, the lifetimes of low-lying vibrational resonances in the predissociative excited state are influenced by tunneling through a small barrier in the dissociation (N–H) coordinate, which is also responsible for a strong H/D isotope effect. The latter, on the other hand, is affected by tunneling through a tight barrier in the exit channel primarily along the H–O dissociation coordinate, which is manifested by the non-Arrhenius rate constant at low temperatures, kinetic isotope effects, and vibrational mode selectivity. In addition, the photodetachment of HOCO− produces metastable HOCO species, the decomposition of which is dominated by deep tunneling to the H + CO2 products. Since both systems are influenced by multidimensional tunneling, an accurate characterization of the dynamics requires a quantum mechanical (QM) treatment, preferably with full dimensionality. In this chapter, we review the recent advances in understanding the effects of tunneling in these two reactive systems.

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Acknowledgments

This work has been supported by the Department of Energy and National Science Foundation. We would also like to thank Joel Bowman, Fleming Crim, Richard Dawes, Evi Goldfield, Don Truhlar, Al Wagner, Daiqian Xie, David Yarkony, and Dong Hui Zhang for many stimulating discussions.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, 87131, USA

    Hua Guo, Jianyi Ma & Jun Li

  2. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan, 610065, China

    Jianyi Ma

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  1. Hua Guo
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Correspondence to Hua Guo .

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  1. Institut Charles GERHARDT - CNRS 5253, Université Montpellier 2, Montpellier Cedex, France

    Fabien Gatti

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Guo, H., Ma, J., Li, J. (2014). Tunneling in Unimolecular and Bimolecular Reactions. In: Gatti, F. (eds) Molecular Quantum Dynamics. Physical Chemistry in Action. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-45290-1_3

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