A DFT Study of the Adsorption and Dissociation of CO on Fe(100): Influence of Surface Coverage on the Nature of Accessible Adsorption States



In the present article, we report adsorption energies, structures, and vibrational frequencies of CO on Fe(100) for several adsorption states and at three surface coverages. We have performed a full analysis of the vibrational frequencies of CO, thus determining what structures are stable adsorption states and characterizing the transition-state structure for CO dissociation. We have calculated the activation energy of dissociation of CO at 0.25 ML (ML=monolayers) as well as at 0.5 ML; we have studied the dissociation at 0.5 ML to quantify the destabilization effect on the CO(α3) molecules when a neighboring CO molecule dissociates. In addition, it is shown that the number and nature of likely adsorption states is coverage dependent. Evidence is presented that shows that the CO molecule adsorbs on Fe(100) at fourfold hollow sites with the molecular axis tilted away from the surface normal by 51.0°. The adsorption energy of the CO molecule is −2.54 eV and the C[BOND]O stretching frequency is 1156 cm−1. This adsorption state corresponds to the α3 molecular desorption state reported in temperature programmed desorption (TPD) experiments. However, the activation energy of dissociation of CO(α3) molecules at 0.25 ML is only 1.11 eV (≈25.60 kcal mol−1) and the gain in energy is −1.17 eV; thus, the dissociation of CO is largely favored at low coverages. The activation energy of dissociation of CO at 0.5 ML is 1.18 eV (≈27.21 kcal mol−1), very similar to that calculated at 0.25 ML. However, the dissociation reaction at 0.5 ML is slightly endothermic, with a total change in energy of 0.10 eV. Consequently, molecular adsorption is stabilized with respect to CO dissociation when the CO coverage is increased from 0.25 to 0.5 ML.