Molecular level properties of the free water surface and different organic liquid/water interfaces, as seen from ITIM...

Molecular dynamics simulations of the interface of water with four different apolar phases, namely water vapour, liquid carbon tetrachloride, liquid dichloromethane (DCM) and liquid dichloroethane (DCE) are performed on the canonical ensemble at 298 K. The resulting configurations are analysed using the novel method of identification of the truly interfacial molecules (ITIM). Properties of the first three molecular layers of the liquid phases (e.g. width, spacing, roughness, extent of the in-layer hydrogen bonding network) as well as of the molecules constituting these layers (e.g., dynamics, orientation) are investigated in detail. In the analyses, particular attention is paid to the effect of the polarity of the non-aqueous phase and to the length scale of the effect of the vicinity of the interface on the various properties of the molecules. The obtained results show that increasing polarity of the non-aqueous phase leads to the narrowing of the interface, in spite of the fact that, at the same time, the truly interfacial layer of water gets somewhat broader. The influence of the nearby interface is found to extend only to the first molecular layer in many respects. This result is attributed to the larger space available for the truly interfacial than for the non-interfacial molecules (as the shapes of the two liquid surfaces are largely independent of each other, resulting in the presence of voids between the two phases), and to the fact that the hydrogen bonding interaction of the truly interfacial water molecules with other waters is hindered in the direction of the interface.