The reconstruction of Rh(001) upon oxygen adsorption

We report on a first-principles study of the structure of O/Rh(001) at half a monolayer of oxygen coverage, performed using density functional theory. We find that oxygen atoms sit at the center of the black squares in, a chess-board c(2 x 2) pattern. This structure is unstable against a rhomboid distortion of the black squares, which shortens the distance between an O atom and two of the four neighboring Rh atoms, while lengthening the distance with respect to the other two. We actually find that the surface energy is further lowered by allowing the O atom to get off the short diagonal of the rhombus thus formed. We predict that the latter distortion is associated with an order-disorder transition, occurring below room temperature. The above rhomboid distortion of the square lattice may be seen as a rotation of the empty white squares. Our findings are at variance with recent claims based on STM images, according to which it is instead the black squares which would rotate. We argue that these images are indeed compatible with our predicted reconstruction pattern. (C) 1998 Elsevier Science B.V. All rights reserved.