Journal of Electroanalytical Chemistry, Vol.420, No.1-2, 209-218, 1997
A Theoretical-Study of the Interaction of Water-Molecules with the Cu(100), Ag(100) and Au(100) Surfaces
The interaction of a water molecule with copper, silver and gold surfaces has been studied using a cluster model approximation. The B3LYP method has been used to introduce a correlation effect into this type of calculation. Since this is a relatively new technique, its performance in conjunction with different basis sets has been tested using the Cu-H2O system as a test case. These tests were performed to select the basis sets for water and metal atoms to be used in studies on the water-metal cluster interaction. Additionally, a set of B3LYP calculations for the Cu-n-H2O (n = 2, 4, 5, 9, 12) systems has been performed to investigate the influence of the metal cluster size on the results. Significant variations in the quantities computed have been found for the smaller clusters, while for the larger ones, a degree of convergence seems to be achieved. Thus, the Cu-12, Ag-12 and Au-12 clusters have been used to mimic the (100) crystallographic plane of noble metals. The comparative results of the water-metal interaction for three different positions (on-top, bridge and hollow) are given; for each site the results for three different orientations of H2O molecule are shown. Two preferred conformations, bridge-perpendicular and top-tilted, have been found to be effectively indistinguishable in terms of adsorption energy; in both, water adsorbs via its oxygen end. For the on-top site, the tilt angle between the H2O molecular plane and the normal to the metal surface has been found to be in the range 50-65 degrees, depending on the metal. The copper has been found to be the most hydrophilic metal (Delta E-ads = -31.8 kJ mol(-1)) when compared with less attractive gold (Delta E-ads = -29.7 kJ mol(-1)) and silver (Delta E-ads = -26.6 kJ mol(-1)). The results obtained from our calculations are compared with some earlier theoretical results and with the experimental data available.
Keywords:EFFECTIVE CORE POTENTIALS;TRANSITION-METAL ATOMS;BASIS-SETS;ORBITAL METHODS;H2O ADSORPTION;CLUSTER MODEL;WORK-FUNCTION;COPPER;PT(111);NI(111)