Optimal ratio or historical convention: the use of methanol–ethanol mixtures as pressure-transmitting mediums

We employ a combined computational and experimental approach to systematically assess the hydrostatic properties of methanol-ethanol (MeOH-EtOH) mixtures of varying compositions, with the aim of evaluating their suitability as pressure-transmitting mediums (PTMs). PTMs are essential for enabling the characterization of materials properties at high pressure, perhaps most prominently in the context of diffraction measurements, to provide uniform compression and avoid strain on the sample. Molecular dynamics (MD) simulations indicate that the hydrostatic limit and several structural and dynamic properties of the widely used 4:1 MeOH-EtOH volume ratio do not exhibit any significant deviations from the monotonic trends observed as a function of MeOH content within the mixture. These findings are in agreement with X-ray pair distribution function measurements, which show no peculiar structural behaviour for the 4:1 composition. Experimental measurements of the hydrostatic limit confirm this result and demonstrate that, as previously reported, the role of ethanol is primarily to delay MeOH crystallization. However, we find that the same role can be fulfilled by other small molecules, such as propan-2-ol. Additional simulations of several MeOH-<i>X</i> binary mixtures suggest that these results might hold for a variety of similar mixtures. Thus, our findings indicate that the 4:1 ratio is neither peculiar nor optimal in terms of PTM performance; instead, its popularity seems to be mostly due to the influence of previous literature. Indeed, we find that the 9:1 MeOH-EtOH mixture is characterized by a hydrostatic limit which is superior (by nearly 1 GPa) to that observed for the 4:1 ratio. These findings offer a promising alternative PTM composition which is readily available, and pave the way towards future work aimed at the rational design of novel PTMs.