We report here experimental results on laser ablation of metals in air and in vacuum in similar irradiation conditions. The experiments revealed that the ablation thresholds in air are less than half those measured in vacuum. Our analysis shows that this difference is caused by the existence of a long-lived transient nonequilibrium surface state at the solid-vacuum interface. The energy distribution of atoms at the surface is Maxwellian-like but with its high-energy tail truncated at the

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... energy. We find that in vacuum the time needed for energy transfer from the bulk to the surface layer to build the high-energy tail, exceeds other characteristic timescales such as the electron-ion temperature equilibration time and surface cooling time. This prohibits thermal evaporation in vacuum for which the high-energy tail is essential. In air, however, collisions between the gas atoms and the surface markedly reduce the lifetime of this nonequilibrium surface state allowing thermal evaporation to proceed before the surface cools. We find, therefore, that the threshold in vacuum corresponds to nonequilibrium ablation during the pulse, while thermal evaporation after the pulse is responsible for the lower ablation threshold observed in air. This paper provides direct experimental evidence of how the transient surface effects may strongly affect the onset and rate of a solid-gas phase transition.