A Jump on Catalyst Kinetics: A common method for interrogating fast reaction kinetics is to create an abrupt initiation point, and, for reactions catalyzed by metals on oxide supports, one option is to induce a rapid temperature jump, provided that the part of the catalyst undergoing heating can be probed locally. Thibault-Starzyk et al. (p. 1048 ) used femtosecond laser pulses to heat catalysts for nitrogen oxide removal and followed the reaction with Fourier-transform infrared spectroscopy. These catalysts are designed to remove NO in fuel-efficient lean-burn engines through reaction with CO, rather than with hydrocarbons. A cyanide reaction intermediate was identified that moves from the silver nanoparticle to the alumina surface.

Ultrafast laser pulses on $\mathrm{Ir}\{111\}$ 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 $2{\pi }^{*}d$ 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.

Adsorbed mercaptopyridine can sense hydrogen-bonding because the ring breathing mode has a different frequency from bare and protonated species.