Reactions on stepped surfaces are relevant to heterogeneous catalysis, in which a reaction often takes place at the edges of nanoparticles where the edges resemble steps on single-crystal stepped... Show moreReactions on stepped surfaces are relevant to heterogeneous catalysis, in which a reaction often takes place at the edges of nanoparticles where the edges resemble steps on single-crystal stepped surfaces. Previous results on H2 + Cu(211) showed that, in this system, steps do not enhance the reactivity and raised the question of whether this effect could be, in any way, related to the neglect of quantum dynamical effects in the theory. To investigate this, we present full quantum dynamical molecular beam simulations of sticking of H2 on Cu(211), in which all important rovibrational states populated in a molecular beam experiment are taken into account. We find that the reaction of H2 with Cu(211) is very well described with quasi-classical dynamics when simulating molecular beam sticking experiments, in which averaging takes place over a large number of rovibrational states and over translational energy distributions. Our results show that the stepped Cu(211) surface is distinct from its component Cu(111) terraces and Cu(100) steps and cannot be described as a combination of its component parts with respect to the reaction dynamics when considering the orientational dependence. Specifically, we present evidence that, at translational energies close to the reaction threshold, vibrationally excited molecules show a negative rotational quadrupole alignment parameter on Cu(211), which is not found on Cu(111) and Cu(100). The effect arises because these molecules react with a site-specific reaction mechanism at the step, that is, inelastic rotational enhancement, which is only effective for molecules with a small absolute value of the magnetic rotation quantum number. From a comparison to recent associative desorption experiments as well as Born–Oppenheimer molecular dynamics calculations, it follows that the effects of surface atom motion and electron–hole pair excitation on the reactivity fall within chemical accuracy, that is, modeling these effect shifts extracted reaction probability curves by less than 1 kcal/mol translational energy. We found no evidence in our fully state-resolved calculations for the “slow” reaction channel that was recently reported for associative desorption of H2 from Cu(111) and Cu(211), but our results for the fast channel are in good agreement with the experiments on H2 + Cu(211). Show less
The HCl + Au(111) system has recently become a benchmark for highly activated dissociative chemisorption, which presumably is strongly affected by electron–hole pair excitation. Previous dynamics... Show moreThe HCl + Au(111) system has recently become a benchmark for highly activated dissociative chemisorption, which presumably is strongly affected by electron–hole pair excitation. Previous dynamics calculations, which were based on density functional theory at the generalized gradient approximation level (GGA-DFT) for the molecule–surface interaction, have all overestimated measured reaction probabilities by at least an order of magnitude. Here, we perform ab initio molecular dynamics (AIMD) and AIMD with electronic friction (AIMDEF) calculations employing a density functional that includes the attractive van der Waals interaction. Our calculations model the simultaneous and possibly synergistic effects of surface temperature, surface atom motion, electron–hole pair excitation, the molecular beam conditions of the experiments, and the van der Waals interaction on the reactivity. We find that reaction probabilities computed with AIMDEF and the SRP32-vdW functional still overestimate the measured reaction probabilities, by a factor 18 for the highest incidence energy at which measurements were performed (≈2.5 eV). Even granting that the experiment could have underestimated the sticking probability by about a factor three, this still translates into a considerable overestimation of the reactivity by the current theory. Likewise, scaled transition probabilities for vibrational excitation from ν = 1, j = 1 to ν = 2 are overestimated by the AIMDEF theory, by factors 3–8 depending on the initial conditions modeled. Energy losses to the surface and translational energy losses are, however, in good agreement with experimental values. Show less
