The c(4×2)-CO/Ni(111) surface under pulsed near-infrared irradiation is examined by time-resolved sumfrequency generation (SFG) spectroscopy. At a surface coverage of 0.5, the surface is confirmed to consist almost exclusively of hollow CO molecules, as evidenced by a sole SFG peak at 1904 cm -1 . Under pulsed irradiation, this peak weakened, followed by the emergence of a new peak attributable to atop CO. This represents a direct observation of site-hopping of adsorbed CO. The hopping phenomenon was found to be entirely transient, with the surface returning to the pre-excited state within a few hundred picoseconds without desorption. The dynamics of the process are also discussed.

The reaction dynamics of trans-2-butene adsorbed to acidic hydroxyl groups on the surface of ferrierite zeolite is examined by time-resolved spectroscopy using a tunable infrared picosecond pulse laser system. The transient absorption spectra measured by a two-color pump-probe technique at 188-243 K reveal bleaching and hot bands of the OD stretching mode 2 ps after excitation. This vibrationally excited state relaxes within 20 ps at 188 K, while the bleaching band includes a long-lifetime component that lasts for more than 100 ps at 243 K. Thus, the OD (isotope-exchanged hydroxy groups) stretching band does not entirely recover in this period and is mirrored by an analogous weakening of the CH bending band of the adsorbed trans-2-butene. Simultaneously, three new bands in CH stretching region were observed at 3045, 3095, and 3130 cm(-1). This result suggests the presence of a short-lived intermediate formed by reaction between the acidic hydroxyl groups and adsorbed trans-2-butene.