Dissociative Electron Attachment on Metal Surfaces: The Case of HCl^- on Au(111)

The transfer of charges, including electrons and holes, is a key step in heterogeneous catalysis, taking part in the reduction and oxidation of adsorbate species on catalyst surfaces. In plasmonic catalysis, electrons can transfer from photo-excited metal nanoparticles to molecular adsorbates, forming transient negative ions that can easily undergo reactions such as dissociation, desorption, or other chemical transformations. However, ab initio characterization of these anionic states has proven challenging, and little is known about the topology of their potential energy surfaces. In this work, we investigate the dissociative adsorption of HCl on Au(111) as a representative catalytic process with relatively low reaction probabilities, which could potentially be enhanced by electron transfer from photo-excited gold nanoparticles to HCl. We employ projection-based density embedding that combines the equation-of-motion electron-attachment coupled-cluster singles and doubles (EOM-EA-CCSD) method with density functional theory (DFT), and build dissociation curves of HCl^- on Au(111) along the H-Cl bond distance. The HCl anion in the gas phase is unbound at equilibrium distances and only becomes bound as the bond stretches. However, our results show that, upon adsorption on Au(111), HCl^- remains a stable, bound anion at all bond lengths due to charge delocalization to the metal. Forming bound anions is easier, and dissociation of HCl^- on Au(111) is further facilitated, with its dissociation energy reduced by 0.61 eV compared to its neutral counterpart on Au(111), and by 1.16 eV relative to HCl. These results underscore the efficacy of embedded EOM-CCSD methods in addressing surface science challenges and highlight the potential of plasmonic catalysis proceeding via bound, rather than transient, anionic states.