CO photodesorption from Pt(111) induced by femtosecond laser pulses is probed by IR+visible sum frequency generation (SFG). Steady state analysis of SFG spectra at varying CO pressure and laser fluence allows one to measure a approximately 5 orders of magnitude decrease of the photodesorption rate constant when CO coverage decreases from 0.37 to 0.07 monolayer. We ascribe this effect in the framework of the Menzel-Gomer-Redhead mechanism to electron delocalization in the CO layer. The lifetime of electronic excitation decreases when coverage decreases.

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http://dx.doi.org/10.1103/PhysRevLett.92.216102DOI Listing

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