Condensed-phase isomerization through tunnelling gateways

Arnab Choudhury, Jessalyn A. DeVine, Shreya Sinha, Jascha A. Lau, Alexander Kandratsenka, Dirk Schwarzer, Peter Saalfrank and Alec M. Wodtke ()
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Arnab Choudhury: University of Goettingen
Jessalyn A. DeVine: Max Planck Institute for Multidisciplinary Sciences
Shreya Sinha: University of Potsdam
Jascha A. Lau: University of Goettingen
Alexander Kandratsenka: Max Planck Institute for Multidisciplinary Sciences
Dirk Schwarzer: Max Planck Institute for Multidisciplinary Sciences
Peter Saalfrank: University of Potsdam
Alec M. Wodtke: University of Goettingen

Nature, 2022, vol. 612, issue 7941, 691-695

Abstract: Abstract Quantum mechanical tunnelling describes transmission of matter waves through a barrier with height larger than the energy of the wave1. Tunnelling becomes important when the de Broglie wavelength of the particle exceeds the barrier thickness; because wavelength increases with decreasing mass, lighter particles tunnel more efficiently than heavier ones. However, there exist examples in condensed-phase chemistry where increasing mass leads to increased tunnelling rates2. In contrast to the textbook approach, which considers transitions between continuum states, condensed-phase reactions involve transitions between bound states of reactants and products. Here this conceptual distinction is highlighted by experimental measurements of isotopologue-specific tunnelling rates for CO rotational isomerization at an NaCl surface3,4, showing nonmonotonic mass dependence. A quantum rate theory of isomerization is developed wherein transitions between sub-barrier reactant and product states occur through interaction with the environment. Tunnelling is fastest for specific pairs of states (gateways), the quantum mechanical details of which lead to enhanced cross-barrier coupling; the energies of these gateways arise nonsystematically, giving an erratic mass dependence. Gateways also accelerate ground-state isomerization, acting as leaky holes through the reaction barrier. This simple model provides a way to account for tunnelling in condensed-phase chemistry, and indicates that heavy-atom tunnelling may be more important than typically assumed.

Date: 2022
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DOI: 10.1038/s41586-022-05451-0

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