State-resolved evidence for hot carrier driven surface reactions: laser-induced desorption of NO from Pt(111)

State-specific diagnostics are used to characterize the laser-induced desorption of NO from Pt(111). Two desorption channels are observed; one is consistent with thermal activation, while the other is driven by adsorbate interactions with hot carriers. For this latter channel, the observed dependence of the desorption yield on the wavelength of the incident laser pulse (1907, 1064, 532, and 355 nm) and the wavelength dependence of the kinetic energy distributions establish the nonthermal nature of the excitation process. The inverted spin–orbit population, the non-Boltzmann rotational state distributions, and the vibrational state population are interpreted in terms of a desorption mechanism involving a temporary ion resonance.