Vibrational Relaxation of Cyanide on Copper Surfaces: Can Metal d-bands Influence Vibrational Energy Transfer?

Abstract

The lifetime for the CN- stretching mode has been measured at a polycrystalline Cu and Cu(111) electrochemical interface with difference frequency generation. The lifetimes on both surfaces are ∼17 ps, show no definitive trend with electrochemical potential, and are similar to those reported for the CN-/Au system. When all experimental lifetimes for CN- on metals are considered, a trend is noted between vibrational lifetime and the onset of metal interband transitions.