Hydroxyl on Stepped Copper and its Interaction with Water.

We describe the hydroxyl and mixed hydroxyl-water structures formed on a stepped copper surface following the reaction of adsorbed O with water at a low temperature and compare them to the structures found previously on plane copper surfaces. Thermal desorption profiles, STM, and low-energy electron diffraction show that water reacts with O at temperatures below 130 K on Cu(511). Two well-defined phases appear as the OH/HO layer is heated to desorb excess water, a 1OH:1HO phase and a pure OH phase. The 1OH:1HO structure consists of 1D chains binding across two adjacent copper steps, with a double period along the step. Electronic structure calculations show that the structure has a zigzag chain of water along the terrace, stabilized by hydrogen bonds to OH groups adsorbed in the step bridge sites. This structure binds OH in its favored site and is similar to the structure observed on other open faces of Cu and Ni, suggesting that this structural arrangement may be common on other surfaces that have steps or rows of close packed metal atoms. The hydroxyl/water chains decompose at 210 K to leave OH adsorbed in the Cu step bridge site, with some forming H-bonded trimers that bridge between two Cu steps. Heating the surface causes hydroxyl to disproportionate near 300 K, desorbing water to leave chemisorbed O.