CO adsorption on CeO2(111): A CCSD(T) benchmark study using an embedded-cluster model

A benchmark model that combines an embedded-cluster approach for ionic surfaces with wavefunction-based methods to predict the vibrational frequencies of molecules adsorbed on surfaces is presented. As a representative case, the adsorption of CO on the lowest index non-polar and most stable facet of CeO2, that is, (111) was studied. The CO harmonic vibrational frequencies were not scaled semiempirically but explicitly corrected for anharmonic effects, which amount to about 25 cm-1 with all tested methods. The second-order Møller-Plesset perturbation method (MP2) tends to underestimate the CO harmonic frequency by about 40-45 cm-1 in comparison with the results obtained with the coupled-cluster singles and doubles with perturbational treatment of triple excitation method [CCSD(T)] and independently from the basis set used. The best estimate for the CO vibrational frequency (low-coverage case) differs by 12 cm-1 with the experimental value obtained by infrared reflexion absorption spectroscopy of 1 monolayer CO adsorbed on the oxidized CeO2(111) surface. In addition, a conservative estimate of the adsorption energy of about -0.22 ± -0.07 eV obtained at the CCSD(T) level confirms the physisorption character of the adsorption of CO on the CeO2(111) surface.