Chlorine chemisorption on Cu(0 0 1) by surface X-ray diffraction: Geometry and substrate relaxation

We report on the precise location of Cl atoms chemisorbed on a Cu(0 0 1) surface and the interlayer relaxations of the metal surface. Previous studies have shown that chlorine dissociates on Cu(0 0 1) to form a c(2 × 2) chemisorbed layer with Cl atoms occupying four-fold hollow sites. A Cu–Cl interlayer spacing of 1.60 Å and a slightly expanded Cu–Cu first interlayer spacing of 1.85 Å (1.807 Å for bulk Cu) was determined by LEED. The resulting Cu–Cl bond length, 2.41 Å, is very similar to the SEXAFS value of 2.37 Å. Contradictory results were obtained by angle-resolved photoemission extended fine structure: while confirming the Cu–Cl interlayer spacing of 1.60 Å, no first Cu–Cu interlayer relaxation has been observed. On the other hand, a small corrugation of the second Cu layer was pointed out. We carried out a detailed structural determination of the Cu(0 0 1)–c(2 × 2)-Cl system using surface X-ray diffraction technique with synchrotron radiation. We find a Cu–Cl interlayer spacing of 1.584(5) Å and confirm the expansion of the first Cu–Cu interlayer, with an average spacing of 1.840(5) Å. In addition, we observe a small corrugation of the second Cu layer, with Cu atoms just below Cl atoms more tightly bound to the surface layer, and even a second Cu–Cu interlayer expansion.