Adsorption of carbon monoxide, CO, on the surface of magnetic Pd13, Pd13–, and Pd13+ clusters, showing magnetic moments of 8, 7, and 7 Bohr magnetons (μB), respectively, was studied by means of density functional methods, allowing partial inclusion of relativistic effects. The favorable adsorption modes are on top, bridge, and threefold, with the binding energy of CO with Pd13– increasing in this same order as 39.4, 48.0 and 50.2 kcal/mol. In addition, the experimental results for the [Pdn–CO]–, n = 4–12, anions show a decrease of the vibrational frequency of CO along this triad of modes, 1940, 1800, and 1680 cm−1, with respect to the free CO value, 2143 cm−1, which conforms to our estimated frequencies, 1956, 1784, and 1679 cm−1, for CO in the [Pd13–CO]– complex. Also, the threefold mode shows a significantly longer bond length for CO, 1.210 Å, with respect to the free case, 1.139 Å. Then the bond of CO is considerably weakened in the negatively charged [Pd13CO]– cluster when the adsorption occurs in a threefold site. These results are mainly accounted for by charge transfer effects from the Pd13 cluster to the CO molecule. Smaller CO activation was found in neutral Pd13–CO and in [Pd13–CO]+, where hollow adsorption yields bigger structural and electronic changes on CO than the respective bridge and on-top modes. Overall, CO adsorption notably quenches the magnetization of neutral and charged Pd13 particles.
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