Direct measurement of core-level relaxation dynamics on a surface-adsorbate system.

The coupling between electronic states in a surface-adsorbate system is fundamental to the understanding of many surface interactions. In this Letter, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By comparing laser-assisted photoemission from a substrate with a delayed Auger decay process from an adsorbate, we measure the lifetime of the 4d(-1) core level of xenon on Pt(111) to be 7.1+/-1.1 fs. This result opens up time-domain measurements of surface dynamics where energy-resolved measurements may provide incomplete information.