Js. Luo et al., CO ON PT(335) - VIBRATIONAL OVERTONES AND SITE DEPENDENCE OF THE VIBRATIONAL STARK-EFFECT, The Journal of chemical physics, 99(2), 1993, pp. 1347-1355
Electron energy loss spectroscopy is used to compare atop CO at two si
tes on Pt(335): on the flat (111) terrace and on the step edge. The cr
oss section for the C-O stretch overtone of the terrace species is not
significantly larger than that of the edge species. Previous experime
nts have shown that the vibrational frequency of terrace CO responds m
uch less to applied electrostatic field than does edge CO, even though
their ir cross sections are about the same. The present experiment sh
ows that CO has similar molecular properties at the two sites: a chemi
cal explanation for the different Stark tuning rates is ruled out. The
difference could be due to spatial variation of the electric field. L
ocal screening of almost all the static electric field at terrace site
s is one possibility, but a simple jellium model is unable to explain
the observed effect. Interaction of the molecular quadrupole moment wi
th the spatially varying field near the surface is also important.