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Highly Efficient Activation of HCl Dissociation on Au(111) via Rotational Preexcitation

[Image: see text] The probability for dissociation of molecules on metal surfaces, which often controls the rate of industrially important catalytic processes, can depend strongly on how energy is partitioned in the incident molecule. There are many example systems where the addition of vibrational...

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Detalles Bibliográficos
Autores principales: Gerrits, Nick, Geweke, Jan, Auerbach, Daniel J., Beck, Rainer D., Kroes, Geert-Jan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8350909/
https://www.ncbi.nlm.nih.gov/pubmed/34313445
http://dx.doi.org/10.1021/acs.jpclett.1c02093
Descripción
Sumario:[Image: see text] The probability for dissociation of molecules on metal surfaces, which often controls the rate of industrially important catalytic processes, can depend strongly on how energy is partitioned in the incident molecule. There are many example systems where the addition of vibrational energy promotes reaction more effectively than the addition of translational energy, but for rotational pre-excitation similar examples have not yet been discovered. Here, we make an experimentally testable theoretical prediction that adding energy to the rotation of HCl can promote its dissociation on Au(111) 20 times more effectively than increasing its translational energy. In the underlying mechanism, the molecule’s initial rotational motion allows it to pass through a critical region of the reaction path, where this path shows a strong and nonmonotonic dependence on the molecular orientation.