Alkali Metal Adsorbates on W(110): Ionic, Covalent, or Metallic?

The photoemission signal from the first atomic layer of W(110) is used to assess the nature of the interaction between the surface atoms of the metal substrate and the adsorbates Na, K, and Cs for coverages up to 1 atomic layer. Our results indicate that there is little or no charge transfer from the alkali metal to the W surface, even in the limit of low coverage. The satellite structure of the photoemission lines of the outermost p shell of the alkali metals confirms this conclusion. While contrary to the conventional picture of alkali-metal-charge donation, these findings fully support recent theoretical calculations

Enhanced Vibrational Broadening of Core-Level Photoemission from the Surface of Na(110)

High-resolution temperature-dependent photoemission data from Na 2p core levels reveal substantially larger phonon broadening in the first atomic layer of Na(110) than in the bulk. We show that the enhanced width is due primarily to the excitation of relatively soft phonon modes perpendicular to the surface. Soft surface-phonon modes also account for previously reported but uninterpreted broadening of transition-metal surface-atom core levels

Anharmonic Surface Vibrations in Photoemission from Alkali Metals

The phonon widths of outermost core-electron photoemission spectra from (110)-oriented overlayers of Na, K, and Rb metals show the expected Debye behavior for the bulk atoms, but significant deviations for the surface atoms. The data indicate a softening of the surface vibrational mode above 200 K. This effect, which is weak in Na but strong in K and Rb, demonstrates that the vibrational mode normal to the surface is anharmonic

Ionicity of Alkali Metal Adsorbates, Reply

A Comment on the Letter by D. M. Riffe et al. Phys. Rev. Lett. 64, 571 (1990)

Chemical and Reconstruction Induced Surface Core-Level Shifts: H on Low-Index W Surfaces

The H-induced shift of the surface-atom core-level binding energy in W(110) is shown to arise from two distinct effects, one chemical in nature and the other structural. The structural shift supports a recently proposed (1p×1) reconstruction that turns on at ∼0.5 monolayer coverage. These new findings are used to provide a self-consistent interpretation of previously reported shifts from H-covered W(111) and W(100) surfaces

Bulk and Surface Singularity Indices in the Alkali Metals

Photoemission data from (110) films of Li, Na, and Rb, in which the signal from the first atomic layer is well resolved, show that the core-hole-screening singularity index is ∼40% larger at the surface than in the bulk for all three metals. This result, which is indicative of the more atomiclike character of metal surface atoms, in general, is particularly large for the alkali metals because their conduction-electron screening is mainly s-like. In addition to quantifying the difference in screening at the surface, the data provide bulk singularity indices of 0.22, 0.16, and 0.14 for Li, Na, and Rb, respectively. These new values are in better agreement with theory and with the threshold exponents than earlier values derived from incompletely bulklike x-ray photoemission data

Nature of the Charge Localized Between Alkali Adatoms and Metal Substrates

Two previously unappreciated features in photoemission spectra from alkali atoms adsorbed on W(110), namely, the sign of the alkali-induced surface-atom core-level shift of the substrate at low coverage and the very large alkali shallow core-hole lifetime width at all coverages, show that the alkali-substrate interaction is not well described by a transfer of alkali charge. Instead, both features point to the formation of a charge cloud between the alkali adatom and substrate that is derived largely from alkali valence states

Different Core-Hole Lifetime and Screening in the Surface of W(110)

High-resolution 4f photoemission spectra from clean W(110) show that the natural lifetime width and the (electron-hole)-pair singularity index are both larger in the first atomic layer than in the bulk. Phonon broadening for the surface and bulk components are smaller than theoretical estimates, and little excess broadening is detected in the surface layer. These findings are very different from the conventional picture of surface-atom core-level line shapes and have implications extending to other systems

Adlayer core-level shifts of random metal overlayers on transition-metal substrates

We calculate the difference of the ionization energies of a core-electron of a surface alloy, i.e., a B-atom in a A_(1-x) B_x overlayer on a fcc-B(001)-substrate, and a core-electron of the clean fcc-B(001) surface using density-functional-theory. We analyze the initial-state contributions and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Data are presented for Cu_(1-x)Pd_x/Pd(001), Ag_(1-x) Pd_x/Pd(001), Pd_(1-x) Cu_x/Cu(001), and Pd_(1-x) Ag_x/Ag(001), changing x from 0 to 100 %. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from the initial-state trends are explained in terms of the change of inter- and intra-atomic screening upon alloying. A possible role of alloying on the chemical reactivity of metal surfaces is discussed.Comment: 4 pages, 2 figures, Phys. Rev. Letters, to appear in Feb. 199