  Chemisorbed molecules at a fuel cell electrode are a very sensitive probe of
the surrounding electrochemical environment, and one that can be accurately
monitored with different spectroscopic techniques. We develop a comprehensive
electrochemical model to study molecular chemisorption at either constant
charge or fixed applied voltage, and calculate from first principles the
voltage dependence of vibrational frequencies -- the vibrational Stark effect
-- for CO adsorbed on close-packed platinum electrodes. The predicted
vibrational Stark slopes are found to be in very good agreement with
experimental electrochemical spectroscopy data, thereby resolving previous
controversies in the quantitative interpretation of in-situ experiments and
elucidating the relation between canonical and grand-canonicaldescriptions of
vibrational surface phenomena.
