Disentangling Multidimensional Nonequilibrium Dynamics of Adsorbates: CO Desorption from Cu(100).

Hot carriers at metal surfaces can drive nonthermal reactions of adsorbates. Characterizing nonequilibrium statistics among various degrees of freedom in an ultrafast time scale is crucial to understand and develop hot carrier-driven chemistry. Here we demonstrate multidimensional vibrational dynamics of carbon monoxide (CO) on Cu(100) along hot-carrier induced desorption studied by using time-resolved vibrational sum-frequency generation with phase-sensitive detection. Instantaneous frequency and amplitude of the CO internal stretching mode are tracked with a subpicosecond time resolution that is shorter than the vibrational dephasing time. These experimental results in combination with numerical analysis based on Langevin simulations enable us to extract nonequilibrium distributions of external vibrational modes of desorbing molecules. Superstatistical distributions are generated with mode-dependent frictional couplings in a few hundred femtoseconds after hot-electron excitation, and energy flow from hot electrons and intermode anharmonic coupling play crucial roles in the subsequent evolution of the non-Boltzman distributions.