UV photostimulated desorption of ammonia from Cu(111)

Upon irradiation with 193 and 308 nm laser light photoinduced desorption of ammonia from Cu(111) was studied at three coverages less than one monolayer (ML). The linear power dependence of the desorption yield and angle‐resolved translational energy distributions of desorbed molecules indicate that desorption occurs due to an electronic excitation rather than a thermal process. Polarization measurements indicate an excitation process which is mediated by hot substrate electrons. The isotope effect, i.e., the ratio of the cross sections for photostimulated desorption (at 193 nm) of NH₃ and ND₃, respectively, decreases from 4.1 ± 1.2 to 1.9 ± 0.5 when the coverage—with respect to the substrate atom density—was raised from ≊0.02 to ≊0.14 ML. The magnitude of this isotope effect suggests that the energy which is required to break the molecule–surface bond is acquired in an intramolecular coordinate during a short‐lived electronic excitation. We propose that for high vibrational excitation on the ground‐state potential energy surface (PES), efficient coupling of the inversion mode with the molecule–surface coordinate leads to desorption. In order to illustrate the suggested desorption mechanism at a semiquantitative level, we performed trajectory calculations on a two‐dimensional model potential energy surface. The results predict that desorption occurs rapidly within a few vibrational periods of the umbrella mode (T_vib∼35 fs)—with comparable energy release into the translational and vibrational degrees of freedom. Ammonia is furthermore expected to desorb in an inverted geometry, i.e., with the hydrogen atoms pointing towards the surface as opposed to the adsorption geometry with the nitrogen end bound to the surface. Angular distributions of flux and mean translational energy are strongly peaked around the surface normal. Their width can be attributed to thermal motions parallel to the surface prior to excitation.