Enhanced photoinduced desorption from metal nanoparticles by photoexcitation of confined hot electrons using femtosecond laser pulses

Strong fluence dependence of photodesorption cross sections is observed in femtosecond laser photodesorption of NO from (NO)₂ on silver nanoparticles, in contrast to femtosecond photodesorption on bulk metals. The time scale of excitation buildup is found to be equal or less than the pulse duration of ∼100fs; NO translational energies are independent of fluence and pulse duration. We propose a nanoparticle-specific nonlinear mechanism in which, due to confinement, strongly nonthermal hot-electron distributions are maintained during the femtosecond pulses, enhancing the normal desorption pathway.