Theoretical investigation of CO interaction with copper sites in zeolites: Periodic DFT and hybrid quantum mechanical/interatomic potential function study

Periodic DFT and combined quantum mechanics/interatomic potential function (QM-pot) models were used to describe the interaction of CO with the Cu + sites in FER. The CO stretching frequencies were calculated using ?CO(CCSD(T))/rCO(DFT) scaling method relating frequencies determined using a high-level quantum-chemical (coupled clusters) method for simple model carbonyls to CO bond lengths calculated using periodic DFT and QM-pot methods for the Cu+-zeolite system. Both periodic DFT and QM-pot models together with ?CO/rCO scaling describe the CO stretching dynamics with the "near spectroscopic accuracy", giving VCO = 2156 cm-1 in excellent agreement with experimental data. Calculations for various Cu+ sites in FER show that both types of Cu+ sites in FER (channel-wall sites and intersection sites) have the same CO stretching frequencies. Thus, the CO stretching frequencies are not site-specific in the CO/Cu+/FER system. The convergence of the results with respect to the model size was analyzed. When the same exchange-correlation functional is used the adsorption energies from periodic DFT and QM-pot are in good agreement (about 2 kcal/mol difference) but substantially larger than those of the experiment. The adsorption energy calculated with the B3LYP functional agrees with available experimental data. The overestimation of the adsorption energy in DFT calculations (periodic or QM-pot) is related to a red-shift of the CO stretching mode, both result from an underestimation of the HOMO(5?)-LUMO(2? *) gap of CO and the consequent overestimation of the Cu+(d)- CO(2?*) back-donation. For the adsorption energy, this can be overcome by the use of hybrid B3LYP exchange-correlation functional. For the frequency calculations, the DFT problem can be overcome by the use of the ?CO(CCSD(T))/rCO(DFT) correlation. Π2005 American Chemical Society.