Temperature dependent structure and dynamics of isopropanol-water liquid mixtures at low alcohol content

TL;DR

This study uses molecular dynamics simulations to analyze how temperature and composition affect the structure and dynamics of low-alcohol-content isopropanol-water mixtures, focusing on hydrogen bonding and ring formations.

Contribution

It demonstrates near-quantitative agreement with experimental data using specific force fields, enabling detailed analysis of hydrogen bond structures and dynamics in these mixtures.

Findings

Hydrogen bond ring formations are significant at higher alcohol concentrations.

HB lifetimes are longer in mixtures than in pure liquids.

Double maxima observed in alcohol-alcohol HB energy distribution.

Abstract

Series of molecular dynamics simulations for 2-propanol-water mixtures, as a function of temperature (between freezing and room temperature) and composition (xip= 0, 0.5, 0.1 and 0.2) have been performed for temperatures reported in the only available experimental structure study. It is shown that when the all-atom OPLS-AA interatomic potentials for the alcohol are combined with the TIP4P/2005 water model then near-quantitative agreement with measured X-ray data, in the reciprocal space, can be achieved. Such an agreement justifies detailed investigations of structural, energetic and dynamic properties on the basis of the simulation trajectories. Here we focus on characteristics related to hydrogen bonds (HB): cluster-, and in particular, ring formation, energy distributions and lifetimes of HB-s have been scrutinized for the entire system, as well as for the water and isopropanol subsystems. It is demonstrated that, similarly to ethanol-water mixtures, the occurrence of 5-membered hydrogen bonded rings is significant, particularly at higher alcohol concentrations. Concerning HB energetics, an intriguing double maximum appears on the alcohol-alcohol HB energy distribution function. HB lifetimes have been found significantly longer in the mixtures than they are in the pure liquids.