Velocity-resolved Laser-induced Desorption for Kinetics on Surface Adsorbates

Most experimental methods for studying the kinetics of surface reactions – for example, temperature programmed desorption (TPD), molecular beam relaxation spectrometry (MBRS) and velocity-resolved kinetics (VRK) – employ detection schemes that require thermal desorption. However, many adsorbates – for example reaction intermediates – never leave the surface under reaction conditions. In this paper, we present a new method to measure adsorbate concentrations on catalytic surfaces and demonstrate its utility for studying thermal desorption kinetics. After a short-pulsed molecular beam deposits CO or NH₃ on Pt (111), the surface is irradiated with an ultrashort laser pulse that induces desorption. Another tightly focused ultrashort laser pulse ionizes the gas-phase molecules by a non-resonant multiphoton process and the ions are detected. This two-laser signal is then recorded as a function of time after the dosing molecular beam pulse and decays exponentially. First-order thermal desorption rate constants are obtained over a range of temperatures and found to be in good agreement with past reports. Ion detection is done mass selectively with ion-imaging, dispersing the gas phase molecules by their velocities. Since laser-induced desorption (LID) produces hyperthermal gas phase molecules, they can be detected with little or no background. This approach is highly surface-specific and exhibits sensitivity below 10⁻⁴ ML coverage. Because the signals are linearly proportional to adsorbate concentration, the method can be employed at lower temperatures than VRK, whose signal is proportional to reaction rate.