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Updated: May 27, 2026

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Published on: July 27, 2018
Electron kinetic energies from vibrationally promoted surface exoemission: evidence for a vibrational autodetachment
Jerry L LaRue1, Tim Schäfer, Daniel Matsiev
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, United States.
Abstract:
We report kinetic energy distributions of exoelectrons produced by collisions of highly vibrationally excited NO molecules with a low work function Cs dosed Au(111) surface. These measurements show that energy dissipation pathways involving nonadiabatic conversion of vibrational energy to electronic energy can result in electronic excitation of more than 3 eV, consistent with the available vibrational energy. We measured the dependence of the electron energy distributions on the translational and vibrational energy of the incident NO and find a clear positive correlation between final electron kinetic energy and initial vibrational excitation and a weak but observable inverse dependence of electron kinetic energy on initial translational energy. These observations are consistent with a vibrational autodetachment mechanism, where an electron is transferred to NO near its outer vibrational turning point and ejected near its inner vibrational turning point. Within the context of this model, we estimate the NO-to-surface distance for electron transfer.
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