Spectroscopic evidence for perturbed NO dimers on oxidized Mo(110)
Journal Article
·
· Journal of Chemical Physics
- Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (United States)
We report herein the first direct experimental evidence of a nitric oxide dimer (NO){sub 2} which is significantly perturbed from gas- and condensed-phase (NO){sub 2} by bonding of one of the nitrosyls to a metal surface. Infrared reflectance absorbance spectroscopy of isotopically mixed overlayers is used to identify the formation of this species from NO adsorption on oxidized Mo(110) and to characterize it as a second-layer NO[{nu}({sup 14}NO)=1871 cm{sup {minus}1}] bound to a surface nitrosyl [{nu}({sup 14}NO)=1728 cm{sup {minus}1}], The spectroscopic signature of this species is a small ({approximately}8 cm{sup {minus}1}) splitting of {nu}(NO) of each of the nitrosyls upon isotopic mixing, rather than the appearance of three different frequencies for {nu}{sub s}(NO) and {nu}{sub a}(NO). The formation of such a dimer on oxidized Mo(110) does {ital not} result in N{endash}N bond formation, in contrast to the evolution of both N{sub 3} and N{sub 2}O via a dinitrosyl intermediate on the same surface. This result suggests that, on surfaces which interact strongly enough with NO to form chemisorbed nitrosyls stable above room temperature, N{endash}N bond formation is favored by surface-bonding of both nitrosyls, rather than coupling via the weak N{endash}N bond of a condensed-phase type (NO){sub 2} dimer. {copyright} {ital 1998 American Institute of Physics.}
- OSTI ID:
- 663692
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 109; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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