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Title: Hot hole-induced dissociation of NO dimers on a copper surface

Abstract

We use reflection-absorption infrared spectroscopy (RAIRS) to study the photochemistry of NO on Cu(110) in the UV-visible range. We observe that the only photoactive species of NO on Cu(110) is the NO dimer, which is asymmetrically bound to the surface. RAIRS shows that photoinduced dissociation proceeds via breaking of the weak N-N bond of the dimer, photodesorbing one NO{sub g} to the gas phase and leaving one NO{sub ads} adsorbed on the surface in a metastable atop position. We model the measured wavelength-dependent cross sections assuming both electron- and hole-induced processes and find that the photochemistry can be described by either electron attachment to a level 0.3 eV above the Fermi energy E{sub F} or hole attachment to a level 2.2 eV below E{sub F}. While there is no experimental or theoretical evidence for an electron attachment level so close to E{sub F}, an occupied NO-related molecular orbital is known to exist at E{sub F}- 2.52 eV on the Cu(111) surface [I. Kinoshita, A. Misu, and T. Munakata, J. Chem. Phys. 102, 2970 (1995)]. We, therefore, propose that photoinduced dissociation of NO dimers on Cu(110) in the visible wavelength region proceeds by the creation of hot holes at the topmore » of the copper d-band.« less

Authors:
;  [1]
  1. Surface Science Research Centre, University of Liverpool, Oxford Road, Liverpool L69 3BX (United Kingdom)
Publication Date:
OSTI Identifier:
22038794
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 135; Journal Issue: 22; Other Information: (c) 2011 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ABSORPTION; ABSORPTION SPECTROSCOPY; COPPER; CROSS SECTIONS; DESORPTION; ELECTRON ATTACHMENT; FERMI LEVEL; INFRARED SPECTRA; METASTABLE STATES; PHOTOCHEMISTRY; PHOTOLYSIS; SURFACES

Citation Formats

Garcia Rey, Natalia, and Arnolds, Heike. Hot hole-induced dissociation of NO dimers on a copper surface. United States: N. p., 2011. Web. doi:10.1063/1.3664861.
Garcia Rey, Natalia, & Arnolds, Heike. Hot hole-induced dissociation of NO dimers on a copper surface. United States. https://doi.org/10.1063/1.3664861
Garcia Rey, Natalia, and Arnolds, Heike. 2011. "Hot hole-induced dissociation of NO dimers on a copper surface". United States. https://doi.org/10.1063/1.3664861.
@article{osti_22038794,
title = {Hot hole-induced dissociation of NO dimers on a copper surface},
author = {Garcia Rey, Natalia and Arnolds, Heike},
abstractNote = {We use reflection-absorption infrared spectroscopy (RAIRS) to study the photochemistry of NO on Cu(110) in the UV-visible range. We observe that the only photoactive species of NO on Cu(110) is the NO dimer, which is asymmetrically bound to the surface. RAIRS shows that photoinduced dissociation proceeds via breaking of the weak N-N bond of the dimer, photodesorbing one NO{sub g} to the gas phase and leaving one NO{sub ads} adsorbed on the surface in a metastable atop position. We model the measured wavelength-dependent cross sections assuming both electron- and hole-induced processes and find that the photochemistry can be described by either electron attachment to a level 0.3 eV above the Fermi energy E{sub F} or hole attachment to a level 2.2 eV below E{sub F}. While there is no experimental or theoretical evidence for an electron attachment level so close to E{sub F}, an occupied NO-related molecular orbital is known to exist at E{sub F}- 2.52 eV on the Cu(111) surface [I. Kinoshita, A. Misu, and T. Munakata, J. Chem. Phys. 102, 2970 (1995)]. We, therefore, propose that photoinduced dissociation of NO dimers on Cu(110) in the visible wavelength region proceeds by the creation of hot holes at the top of the copper d-band.},
doi = {10.1063/1.3664861},
url = {https://www.osti.gov/biblio/22038794}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 135,
place = {United States},
year = {Wed Dec 14 00:00:00 EST 2011},
month = {Wed Dec 14 00:00:00 EST 2011}
}