Computer simulation of adhesion between hydrophilic and hydrophobic self-assembled monolayers in water.
The grand canonical Monte Carlo technique and atomistic force fields are used to calculate the force-distance relations and free energies of adhesion between carboxyl and methyl terminated alkanethiolate self-assembled monolayers (SAMs) in water. Both symmetric and asymmetric confinements are considered, as formed by like and unlike SAMs, respectively. As the confinement is increased, water confined by the hydrophobic methyl terminated SAMs experiences capillary evaporation. As a consequence, the adhesion energy is determined by the direct interaction between bare SAMs. In the asymmetric system, an incomplete capillary evaporation is observed, with the number of water molecules dropped by more than an order of magnitude. The remaining water molecules are all adsorbed on the hydrophilic SAM, while the hydrophobic SAM is separated from the rest of the system by a thin vapor layer. The calculated free energies of adhesion are in acceptable agreement with experiment.
Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany. sascha.pertsin@urz.uni-heidelberg.de
Alexander
A
Pertsin
Michael
M
Grunze
D000327:Adsorption; D000473:Alkanes / Q000737:chemistry*; D003198:Computer Simulation; D057927:Hydrophobic and Hydrophilic Interactions; D009010:Monte Carlo Method; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
D000473:Alkanes; D014867:Water