Ab initio calculations of CO physisorption on ceria(111)

Abstract: Applying the method of increments, we have performed MP2 and CCSD(T) calculations for the physisorption of CO on a cerium site on the ceria(111) surface. Our calculations predict an interaction energy of −0.28eV. We have compared our calculations to previous CCSD(T) calculations for the physisorption of CO on a cerium site on the ceria(110) surface and found a difference in the interaction energy that is related to the different structure of the two surfaces. On the ceria(110) surface only 30% of the interaction energy originate from electron correlation effects, but on the ceria(111) surface almost the entire binding energy (80%) is due to electron correlation effects. Analyses of the interaction energy contributions show that most of the electron correlation part originates from the interaction of CO with the O ions in the topmost surface layer. [Copyright &y& Elsevier]