Water between plates in the presence of an electric field in an open system.
Molecular dynamics simulations of water at 298 K and 1 atm of pressure are used to investigate the electric-field dependence of the density and polarization density of water between two graphite-like plates of different sizes (9.8 x 9.2 and 17.7 x 17.2 A) in an open system for plate separations of 8.0, 9.5, and 16.4 A. The interactions with water were tuned to "hard-wall-like" and "normal" C-O hydrophobic potentials. Water between the larger plates at 16.4 A separation is layered but is metastable with respect to capillary evaporation at zero field (Bratko, D.; Curtis, R. A.; Blanch, H. W.; Prausnitz, J. M. J. Chem. Phys. 2001, 115, 3873). Applying a field decreases the density of the water between the plates, in apparent contradiction to thermodynamic and integral equation theories of bulk fluid electrostriction that ignore surface effects, rendering them inapplicable to finite-sized films of water between hydrophobic plates. This suggests that the free energy barrier for evaporation is lowered by the applied field. Water, between "hard-wall-like" plates at narrower separations of 9.5 A and less, shows a spontaneous but incomplete evaporation at zero field within the time scale of our simulation. Evaporation is further enhanced by an electric field. No such evaporation occurs, on these time scales, for the smaller plates with the "hard-wall-like" potential at a separation of 8.0 A at zero field, signaling a crossover in behavior as the plate dimension decreases, but the water density still diminishes with increasing field strength. These observations could have implications for the behavior of thin films of water between surfaces in real physical and biological systems.
Vaitheeswaran
Subramanian
S
Department of Physics and Astronomy and Department of Chemistry, University of Maine, Orono, Maine 04469, USA.
Yin
Hao
H
Rasaiah
Jayendran C
JC