Abstract
Chromium hexacarbonyl (Cr(CO) 6) and cyclopentadienyl rhodium dicarbonyl (( η 5 − C 5H 5)Rh(CO) 2) were physisorbed on the Cu(100) surface and their molecular orientations were deduced from their reflection-absorption infrared (RAIR) spectra. No thermal decomposition of the compounds was observed. Physisorbed Cr(CO) 6 exhibited a substantial degree of dipole-dipole coupling within the adlayer, which was successfully disrupted by coadsorption in Ar at 23 K. The large absorption coefficient of the T 1u mode and the different boundary conditions of this ultrathin layer on a surface resulted in the observation of the longitudinal optical mode, confirming that the molecule is oriented with one carbonyl group adjacent to the surface. A Lyndane-Sachs-Teller splitting of 75 cm −1 was observed for the T 1u mode. The physisorbed layer of ( η 5 − C 5H 5)Rh(CO) 2 did not exhibit strong dipole-dipole coupling, and was oriented with the C 5H 5 (Cp) ring parallel to the surface.
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