NMR measurements were performed with nuclear-spin-polarized alkali-metal atoms ( 6 Li, 7 Li, 23 Na) adsorbed on a clean and an oxygen-covered W(110) surface. For the desorbed alkali-metal ions the change of polarization due to the radio-frequency field was detected by beam-foil spectroscopy. Energy splittings of the nuclear states were found arising from the interaction of nuclear quadrupole moments with electric field gradients. They reflect the spatial charge distribution in the vicinity of the adsorbed alkali-metal atoms.PACS numbers: 68.10Jy, 76.60.Gv The interaction of atoms and molecules with solid surfaces has been of general interest for many years. Although a variety of experimental methods has been developed, there is nevertheless a lack of methods which directly probe spatial charge distributions of surfaces and adsorbed atoms. The electronic charge distribution is of particular interest. It is, for example, the basic quantity of one of the most important theoretical methods used for the calculation of surface properties and chemisorption processes, namely the density-functional theory. 1 ' 2 Such calculations require a detailed experimental check.In solids, liquids, and chemical systems, NMR studies turned out to be one of the most powerful techniques for obtaining such microscopic information. However, the application of these methods to solid surfaces is limited, 3 primarily for the following reasons. Conventional NMR measurements, which are based on the very small nuclear polarization governed by the Boltzmann distribution for the nuclear m substates, need a considerable number of probe nuclei. These are not available for systems which are most interesting in surface physics studies, i.e., single-crystal surfaces with a low adsorbate coverage. Moreover, it is in general difficult to distinguish between the bulk and the surface signal. 4 We have developed a NMR technique for which these two difficulties do not arise. This will be demonstrated for alkali-metal atoms (Li, Na) adsorbed on a clean and an oxygen-covered W(110) surface. The principle of our method is as follows (Fig. 1). A thermal alkali-metal atom beam is nuclear-spin polarized by use of a sextupole magnet and a subsequent adiabatic radio-frequency transition, 5 which determines the initial nuclear-spin polarization of the atomic beam. The fact that the probe atoms are prepared in a source means that the polarization is large. Because we do not utilize the Boltzmann distribution for the nuclear m substates, we need neither low temperatures nor high magnetic fields at the surface. The thermal nuclear-spin-polarized alkali-metal atom beam impinges on the surface to be investigated which is kept at temperatures of 1000 to 1500 K in ultrahigh vacuum. The sample is mounted between two coils which produce the rf field. The surface coverage with alkali-metal atoms was in all cases less than 10" 3 of a monolayer. The alkali-metal atoms get desorbed from the surface partly as neutral atoms, partly as positive ions. Only the positive ions are us...