Aqueous-alcohol mixtures in dimension two: miscibility and micro-segregation

Abstract

Two dimensional site interaction models of water and alcohols are mixed in various proportions and studied by Monte Carlo simulations, with the purpose to clarify problems related to simulation of real micro-heterogeneous systems. Three alcohols are considered, methanol, pentanol and octanol. The main finding is that, while real alcohols demix with water from butanol onward, their 2D analogs are always fully miscible, while developing increasingly pronounced micro-segregation as the alcohol tail length increases. This is not a consequence of the intrinsically higher fluctuations in 2D, but rather a reorganization of these fluctuations under the charge ordering mechanism. The second finding is that water drives the micro-segregation through strong self-aggregation, but this is not enough to achieve full phase separation because of the water-alcohol contact at the outer rim of the water domains. In this work we examine how this local heterogeneity develops with increasing alcohol alkyl tails, monitored with the study of pair correlation functions, structure factors and Kirkwood-Buff integrals. The absence of clear local self-averaging of the latter provides an illustration of the tension between energy driven maintaining of local structures and entropy driven global homogeneity. In that, the 2D modelisation of real hydrogen bonding mixtures allows to better capture and reveal the physics behind the chemistry of these liquids.