Electron kinetic energies from vibrationally promoted surface exoemission: Evidence for a vibrational autodetachment mechanism

Jerry L. LaRue, Tim Schaefer, Daniel Matsiev, Luis Velarde, N. Hendrik Nahler, Daniel J. Auerbach, Alec M. Wodtke

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)14306-14314
Number of pages9
JournalJournal of Physical Chemistry A
Volume115
Issue number50
DOIs
Publication statusPublished - 22 Dec 2011

Cite this

LaRue, Jerry L. ; Schaefer, Tim ; Matsiev, Daniel ; Velarde, Luis ; Nahler, N. Hendrik ; Auerbach, Daniel J. ; Wodtke, Alec M. / Electron kinetic energies from vibrationally promoted surface exoemission: Evidence for a vibrational autodetachment mechanism. In: Journal of Physical Chemistry A. 2011 ; Vol. 115, No. 50. pp. 14306-14314.
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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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Electron kinetic energies from vibrationally promoted surface exoemission: Evidence for a vibrational autodetachment mechanism. / LaRue, Jerry L.; Schaefer, Tim; Matsiev, Daniel; Velarde, Luis; Nahler, N. Hendrik; Auerbach, Daniel J.; Wodtke, Alec M.

In: Journal of Physical Chemistry A, Vol. 115, No. 50, 22.12.2011, p. 14306-14314.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electron kinetic energies from vibrationally promoted surface exoemission: Evidence for a vibrational autodetachment mechanism

AU - LaRue, Jerry L.

AU - Schaefer, Tim

AU - Matsiev, Daniel

AU - Velarde, Luis

AU - Nahler, N. Hendrik

AU - Auerbach, Daniel J.

AU - Wodtke, Alec M.

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AB - 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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