Theoretical treatment of excited electronic states of adsorbates on metals: Electron attachment to CO2 adsorbed on K-modified Pt(1 1 1)

Theoretical studies of photoinduced processes involving electron attachment to CO2 adsorbed on Pt(1 1 1) in the presence of a coadsorbed K atom are reported. First principles theoretical methods suitable for describing electronic states embedded in a near continuum of metal to metal excitations are described. Wave functions are constructed by ab initio configuration interaction methods which allow a rigorous resolution of states and differentiation between competing pathways of molecular desorption and dissociation. An embedding theory is used to achieve high accuracy in the adsorbate-surface region. Compared to CO2 adsorbed on Pt(1 1 1), the K promoter lowers the work function of the system from 5.6 to 5.2 eV and decreases the energy required to form the electron attached excited electronic state from 6.8 to 5.6 eV. However, stabilization of CO2 depends strongly on orientation and proximity to the K adatom. The most favorable pathway leading to dissociation requires that CO2 be adsorbed at a site that does not share Pt atoms with the K adsorption site, i.e., at next-nearest neighbor sites. As was found for Pt(1 1 1) without a K adatom, the dissociation pathway involves bending of CO2 in the excited state followed by possible dissociation on the excited state surface where the barrier height is reduced from its value of 1.0 eV on the Pt surface to 0.34 eV. As is the case for the unmodified surface, dissociation could also occur after return to the ground state potential energy surface via vibrational processes.