ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We have used the large electric fields at the interface of a Pt(111) electrode and an acetonitrile electrolyte solution to tune the interaction between adsorbed CO and the Pt(111) surface. The electrode potential is varied over a 2.5 Volt range. As the electrode potential is made more positive, the CO vibrational frequency increases and the vibrational lifetime decreases. Over the potential range investigated, the tuning is about 35–40 cm−1 and the lifetime varies from ≈2.1 to ≈1.5 ps. Ab initio calculations performed for CO/Cu(100) predicted the opposite trend for the lifetimes for that system [M. Head-Gordon and J. C. Jully, Chem. Phys. 175, 37 (1993)]. Within an empirical model of nonadiabatic charge transfer [B. N. J. Persson and M. Persson, Solid State Commun. 36, 175 (1980)], our observations can be explained by a decreasing 2π-derived density of states of the Pt/CO complex at the Fermi level. © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.470938
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