entropy of stronghstrong o wetting layers - university of cambridge.pdfVIP

14362 J. Phys. Chem. B 2004, 108, 1436214367 Entropy of H2O Wetting Layers† Peter J. Feibelman*,‡ and Ali Alavi§ Sandia National Laboratories, Albuquerque, New Mexico 87185-1413 and Department of Chemistry, Uniersity of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom Recei ed: January 6, 2004; In Final Form: April 26, 2004 Proton order is less constrained in a fully H-bonded, adsorbed H2O monolayer than in bulk ice. Thus, though weakly, configurational entropy favors wetting by deposited H2O over formation of 3-D crystalline mounds. A Pauling-type estimate yields a 0 K adlayer entropy of 1/ k ln(9/2), almost twice that of ice Ih. Thus, at 2 B 150 K, where periodic adlayers on metals are observed, residual entropy reduces their free energies relative to a 3-D ice crystal by 4.5 meV/molecule, or 3% of the cost of the adlayers’ broken H-bonds. A Debye model implies that vibrational entropy contributes no more than another 4.4 meV/molecule to the free energy preference for wetting, at 150 K. This information, though only a bound because of substantial uncertainty in measured adlayer Debye temperatures, is nonetheless sufficient to conclude that T 0 K energies dominate the free energy balance between wetting and mound formation. I. Introduction The need to count the low-energy configurations of a proton- disordered, hydrogen-bonded crystal like ice Ih to evaluate its configurational entropy has spawned the development of “ice models” and studies of their subtle correlations. Though typically two-dimensional, suc