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Condensed-phase isomerization through tunnelling gateways

MPS-Authors
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Choudhury,  Arnab
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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DeVine,  Jessalyn
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Lau,  Jascha Alexander
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Kandratsenka,  Alexander       
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Schwarzer,  Dirk       
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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Wodtke,  Alec M.       
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society;

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s41586-022-05451-0.pdf
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Citation

Choudhury, A., DeVine, J., Sinha, S., Lau, J. A., Kandratsenka, A., Schwarzer, D., et al. (2022). Condensed-phase isomerization through tunnelling gateways. Nature, 612, 691-695. doi:10.1038/s41586-022-05451-0.


Cite as: https://hdl.handle.net/21.11116/0000-000C-34C2-E
Abstract
Quantum mechanical tunnelling describes transmission of matter waves through a barrier with height larger than the energy of the wave. 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 rates. 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 surface, 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.