skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Vibrational spectroscopic evidence for (NO){sub 3} formation on Cu(111)

Abstract

The formation of (NO){sub 3} on Cu(111) was recently reported based on scanning tunneling microscopy observations [A. Shiotari et al., J. Chem. Phys. 141, 134705 (2014)]. We herein report studies into this system using electron energy loss spectroscopy and verify the above findings through vibrational analysis. For the surface covered with mixed isotopes of N{sup 16}O and N{sup 18}O, we observed four peaks corresponding to N-O stretching vibrations, which were ascribed to the four isotopic combinations of the trimer. Dynamic coupling within the trimer was evaluated from model calculations of the coupled oscillators. Furthermore, we observed hindered rotation and translation modes in the dipole scattering regime, suggesting that the molecular axis is tilted from the surface normal. These results provide spectroscopic support for the formation of (NO){sub 3} on Cu(111).

Authors:
; ; ;  [1]
  1. Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)
Publication Date:
OSTI Identifier:
22679036
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 5; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATALYST SUPPORTS; COPPER; CRYSTAL LATTICES; CRYSTALS; ENERGY LOSSES; ENERGY-LOSS SPECTROSCOPY; EXPERIMENTAL DATA; ISOTOPES; SCANNING TUNNELING MICROSCOPY; SURFACES; TUNNEL EFFECT

Citation Formats

Koshida, H., Okuyama, H., E-mail: hokuyama@kuchem.kyoto-u.ac.jp, Hatta, S., and Aruga, T. Vibrational spectroscopic evidence for (NO){sub 3} formation on Cu(111). United States: N. p., 2016. Web. doi:10.1063/1.4960053.
Koshida, H., Okuyama, H., E-mail: hokuyama@kuchem.kyoto-u.ac.jp, Hatta, S., & Aruga, T. Vibrational spectroscopic evidence for (NO){sub 3} formation on Cu(111). United States. doi:10.1063/1.4960053.
Koshida, H., Okuyama, H., E-mail: hokuyama@kuchem.kyoto-u.ac.jp, Hatta, S., and Aruga, T. Sun . "Vibrational spectroscopic evidence for (NO){sub 3} formation on Cu(111)". United States. doi:10.1063/1.4960053.
@article{osti_22679036,
title = {Vibrational spectroscopic evidence for (NO){sub 3} formation on Cu(111)},
author = {Koshida, H. and Okuyama, H., E-mail: hokuyama@kuchem.kyoto-u.ac.jp and Hatta, S. and Aruga, T.},
abstractNote = {The formation of (NO){sub 3} on Cu(111) was recently reported based on scanning tunneling microscopy observations [A. Shiotari et al., J. Chem. Phys. 141, 134705 (2014)]. We herein report studies into this system using electron energy loss spectroscopy and verify the above findings through vibrational analysis. For the surface covered with mixed isotopes of N{sup 16}O and N{sup 18}O, we observed four peaks corresponding to N-O stretching vibrations, which were ascribed to the four isotopic combinations of the trimer. Dynamic coupling within the trimer was evaluated from model calculations of the coupled oscillators. Furthermore, we observed hindered rotation and translation modes in the dipole scattering regime, suggesting that the molecular axis is tilted from the surface normal. These results provide spectroscopic support for the formation of (NO){sub 3} on Cu(111).},
doi = {10.1063/1.4960053},
journal = {Journal of Chemical Physics},
number = 5,
volume = 145,
place = {United States},
year = {Sun Aug 07 00:00:00 EDT 2016},
month = {Sun Aug 07 00:00:00 EDT 2016}
}
  • Reaction of {sup 63}Cu atoms with CO has been studied in inert hydrocarbon matrices in a rotating cryostat at 77 K at EPR, FTIR, and UV/visible spectroscopy. CuCO and Cu(CO){sub 3} have been identified by EPR spectroscopy. CuCO has the magnetic parameters a{sub 63} = 3961 MHz, a{sub 13} = 191 MHz, and g = 1.9966 and is a linear molecule with most of the unpaired spin located in an sp-hybridized orbital on Cu. It is unstable and disappears rapidly above 77 K. Cu(CO){sub 3} is a planar trigonal {pi} radical with a {sup 2}A{sub 2}{prime}{prime} electronic ground state andmore » a{sub 17} = 11.2 MHz which indicates significant unpaired spin population on the ligands. It has three infrared bands at 1998, 1988, and 1978 cm{sup {minus}1} which are assigned to the CO stretching mode of a D{sub 3h} molecule in three different trapping sites and is significantly more stable than CuCO. There are no bands in the FTIR spectra from Cu(CO){sub 2}. Cu{sub 2}(CO){sub 6} is formed in significant yields in adamantane and cyclohexane at 77 K and has a major CO stretching mode at 2035 cm{sup {minus}1}. Optical spectra of Cu(CO){sub 3} and Cu{sub 2}(CO){sub 6} in adamantane have {sup 2}A{sub 1}{prime} {l arrow} {sup 2}A{sub 2}{prime}{prime} and {sigma}* {l arrow} {sigma} electronic transitions at 565 and 405 nm, respectively.« less
  • Adsorption of tetracyanoethylene (TCNE) on a Cu(111) single surface at 100 K has been studied by high-resolution electron energy loss spectroscopy. Upon initial adsorption there is spectroscopic evidence for partial fragmentation of TCNE molecules. For increasing coverages up to one monolayer, a multiply charged TCNE ion is identified as the dominant species on the copper surface. Further exposure to TCNE produces vibrational modes characteristic of TCNE anions, most likely adsorbed in a second layer. Finally, multilayer condensation for high exposures is indicated by the observation of virtually all vibrational modes of crystalline TCNE.
  • Ion channeling along the /ital c/ axis in ErBa/sub 2/Cu/sub 3/O/sub 7/minus//delta// reveals a normal (Debye-type) temperature dependence for thermal vibrations of the Er and Ba atoms between 40 and 300 K. In contrast, a substantially stronger than normal temperature dependence is found for the Cu-O atom vibrations, and a large, anomalous change (/similar to/30%) is seen at the superconducting transition. The large magnitude of the vibrational changes found for the Cu-O rows across /ital T//sub /ital c// suggests that the atoms in these rows become strongly coupled in the superconducting state.
  • The formation of crystalline ice through isothermal heating of 80 layers amorphous ice on Pt(111) at 150 K is studied using X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy. An early indicator for inhomogeneous crystallization is provided by the uncharacteristically high Pt 4f photoelectron peak for crystalline ice compared with the corresponding uniformly thick amorphous case. O 1s photoelectron spectra unambiguously show that the first monolayer is exposed after crystallization at multilayer total coverage. Using the relative intensities between the first monolayer and multilayer contributions to the O 1s photoelectron spectra, we estimated that -46% and -80% of the firstmore » monolayer is exposed to vacuum with an average crystallite height of -41 and -31 layers for an equivalent total coverage of -23 and -7 layers, respectively.« less
  • Perturbed angular correlation (PAC) spectroscopy has been used to measure a well-defined static electric quadrupole interaction in a superconducting ceramic, In/sub 0.1/Y/sub 0.9/Ba/sub 2/Cu/sub 3/O/sub 9-//sub delta/. Perturbation functions, Fourier transforms, and the derived PAC parameters are given for data taken at temperatures ranging from 77 to 1070 K. Indirect evidence is presented for the occupation of the Y site by the /sup 111/In-/sup 111/Cd PAC probe. The derived electric field gradients were found to increase linearly with temperature. This result suggests the presence of soft, anisotropic vibrations in the structure. Additional evidence is presented to indicate that O/sup 2-/-ionmore » or O-vacancy transport may not occur in the Y coordination sphere.« less