Molecular Structural Dynamics in Water-Ethanol Mixtures: Spectroscopy with Polarized Neutrons Simultaneously Accessing Collective and Self-Diffusion

TL;DR

This study uses polarized neutron spectroscopy with deuteration to explore the molecular dynamics and clustering behavior in water-ethanol mixtures, revealing increased hydrogen bond rigidity with higher ethanol content.

Contribution

It introduces a novel combined neutron spectroscopy and deuteration approach to simultaneously analyze collective and self-diffusion in water-ethanol mixtures.

Findings

Enhanced hydrogen bond network rigidity with increased ethanol fraction

Evidence supporting cluster formation at mesoscopic scales

Differentiation of collective and self-diffusion processes

Abstract

Binary mixtures of water with lower alcohols display non-linear phase behaviour upon mixing which are attributed to potential cluster formation at molecular level. Unravelling such elusive structures requires the investigation of hydrogen-bonding sub-nanosecond dynamics. We employ high-resolution neutron time-of-flight spectroscopy with polarization analysis in combination with selective deuteration to study the concentration-dependent structural dynamics, in the water rich part of the phase diagram of water-ethanol mixtures. This method enables the simultaneous access to atomic correlations in space and time, and allows us to separate spatially incoherent scattering probing self-diffusion of the ethanol fraction from the coherent scattering probing collective diffusion of the water network as a whole. Our observations indicate an enhanced rigidity of the hydrogen bond network at mesoscopic lengthscale compared to the intra-molecular scale as the ethanol fraction increases, which is consistent with the hypothesis of clusters.