Microscopic Insight into Electron-Induced Dissociation of Aromatic Molecules on Ice

Auburger, P. and Kemeny, I. and Bertram, C. and Ligges, M. and Bockstedte, M. and Bovensiepen, U. and Morgenstern, K.

Volume: 121 Pages:
DOI: 10.1103/PhysRevLett.121.206001
Published: 2018

We use scanning tunneling microscopy, photoelectron spectroscopy, and ab initio calculations to investigate the electron-induced dissociation of halogenated benzene molecules adsorbed on ice. Dissociation of halobenzene is triggered by delocalized excess electrons attaching to the π∗ orbitals of the halobenzenes from where they are transferred to σ∗ orbitals. The latter orbitals provide a dissociative potential surface. Adsorption on ice sufficiently lowers the energy barrier for the transfer between the orbitals to facilitate dissociation of bromo- and chloro- but not of flourobenzene at cryogenic temperatures. Our results shed light on the influence of environmentally important ice particles on the reactivity of halogenated aromatic molecules. © 2018 American Physical Society.

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