ELECTRONIC CHARGE-DENSITY TRANSFER ALONG A CONSTRAINED REACTION-PATH FROM A HYDRONIUM ION CONFIGURATION INTO A HYDROGEN CHEMISORPTION STATEON CU(100)

On supermolecular models of a hydrogen reaction intermediate on Cu(100 ), we have investigated structural transformations and electronic char ge density transfer along a constrained proton transfer path from a hy drated hydronium ion configuration into a H(ad) state. Computations we re carried out on MP2 level on closed shell model systems Cu-9/H5O2 an d Cu-9/H9O4, using Gaussian (3s2p5d) valence basis set and ECPs for Cu , and DZP(d,p) for O and H atoms. A charge transfer from initial to fi nal adsorbate state respectively from +1 to a significantly negative v alue, and coupled nuclear motion patterns including water reorientatio ns near H(ad) have been proved under 2D-freedom of the constrained rea ction path.