CO/Rh(111): Vibrational frequency shifts and lateral interactions in adsorbate layers

被引:71
作者
Linke, R [1 ]
Curulla, D [1 ]
Hopstaken, MJP [1 ]
Niemantsverdriet, JW [1 ]
机构
[1] Eindhoven Univ Technol, Schuit Inst Catalysis, NL-5600 MB Eindhoven, Netherlands
关键词
D O I
10.1063/1.1355767
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
High resolution electron energy loss spectroscopy (HREELS), low-energy electron diffraction (LEED), and thermal desorption spectroscopy (TDS) were used to study lateral interactions in the adsorbate layer of the CO/Rh(111) system. The vibrational spectra show that CO adsorbs exclusively on top at low coverage. At about half a monolayer a second adsorption site, the threefold hollow site, becomes occupied as well. A steady shift to higher frequencies of the internal C-O vibrations is observed over the whole coverage range. The frequency of the metal CO (M-CO) vibration in the on-top mode hardly shifts at low coverage. However, upon the emergence of the second adsorption site the M-CO vibrations experience a shift to lower frequencies. The population of the second site is also accompanied by the development of a low temperature shoulder in the TD spectra, indicating an increasingly repulsive interaction in the adsorbed CO layer. Vibrational spectra of isotopic mixtures of (CO)-C-12 and (CO)-C-13 were used to assess the origin of the observed frequency shifts. They confirm that frequency shifts of the C-O stretching vibration at total CO coverage of 0.33 ML in the (root 3x root3)R30 degrees structure arise purely from dipole-dipole coupling. Dilution of an isotopic species effectively suppresses frequency shifts arising from dipole-dipole coupling. Therefore, experiments with a small amount of (CO)-C-13 as a tracer to monitor the frequency shifts in the (CO)-C-12 adlayer were carried out over the entire coverage range of (CO)-C-12. The results demonstrate that dipole-dipole coupling causes the frequency shifts at low coverage (<0.5 ML), whereas chemical effects set in at higher coverage (0.5-0.75 ML), connected with the population of the threefold sites. The results illustrate that HREELS in combination with isotopic dilution is a powerful tool in the assessment of lateral interactions between adsorbed molecules. (C) 2001 American Institute of Physics.
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页码:8209 / 8216
页数:8
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