CO Chemisorption at Metal Surfaces and Overlayers

Abstract

A database of ab initio calculations of the chemisorption energy of CO over Ni(111), Cu(111), Ru(0001), Pd(111), Ag(111), Pt(111), Au(111), $\mathrm{Cu}{}_{3}$Pt(111), and some metallic overlayer structures is presented. The trends can be reproduced with a simple model describing the interaction between the metal $d$ states and the CO $2{\ensuremath{\pi}}^{*}$ and 5 $\ensuremath{\sigma}$ states, renormalized by the metal $\mathrm{sp}$ continuum. Our model rationalizes the results by Rodriguez and Goodman [Science 257, 897 (1992)] showing a strong correlation between the CO chemisorption energy and the surface core level shift.