Extended muffin-tin orbital theory applied to the reaction of CO+ H 2 on Ni(001)

The method using energy bands from a linear combination of muffin-tin orbitals has been extended so that the unit cell is now divided into muffin-tin and non-muffin-tin regions, instead of atomic Wigner-Seitz cells. The full potential including the nonspherical contribution to the potential is still included throughout the unit cell. The new method has been applied to the interaction of CO+${\mathrm{H}}_{2}$ on Ni(001) surface. Through use of three-dimensional charge-density plots, we show that CO forms C+C${\mathrm{O}}_{2}$ through disproportionation. We also show that the Ni(001) surface can break the carbon-oxygen bond of formaldehyde, but not carbon monoxide.