Carbide induced reconstruction of monatomic steps on Ni(111) - A density functional study

We present density functional calculations for carbon adsorption at the two types of monatomic steps on a Ni(111) surface. We show that it is thermodynamically favourable to make a carbon induced clock-type reconstruction at the close-packed step with a [111] step geometry, which creates fourfold sites at the step-edge. It is furthermore possible to extend the carbide with the clock reconstructed geometry onto the upper terrace with a net energy gain compared to adsorption of carbon on unreconstructed close-packed steps or terrace sites on Ni(111). Our findings explain the fact that carbide islands start to grow preferentially on the close-packed steps as has been observed using scanning tunneling microscopy.