Real-time observation of nonadiabatic surface dynamics: the first picosecond in the dissociation of NO on iridium.
Ultrafast laser pulses on Ir{111} cause a highly temperature-dependent redshift of the intramolecular stretch frequency of adsorbed NO. The time-resolved spectral changes are driven by charge transfer of hot electrons to the NO 2pi*d antibonding orbital, which leads to bending of NO and internal bond weakening. The nonadiabatic change in the NO adsorption geometry follows the charge transfer within a time scale of 700 femtoseconds. This geometrical change is the same as the mechanism predicted for thermally induced dissociation.
Lane
Ian M
IM
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
King
David A
DA
Liu
Zhi-Pan
ZP
Arnolds
Heike
H