Role of Molecular Structure in Defining the Dynamical Landscape of Deep Eutectic Solvents at Nanoscale

TL;DR

This study investigates how alkyl chain length influences the nanoscale dynamics of deep eutectic solvents, revealing complex relationships between molecular structure and transport properties through neutron scattering and simulations.

Contribution

It provides new insights into how molecular structure, specifically alkyl chain length, affects the nanoscale diffusion and localized dynamics in DESs using combined experimental and computational methods.

Findings

Acetamide shows lowest mobility despite shorter chain.

Long-range jump diffusion is fastest in ACM and slowest in BUT.

PRM exhibits the fastest localized dynamics, ACM the slowest.

Abstract

The molecular dynamics of deep eutectic solvents (DESs) are complex, characterized by nanoscale spatial and temporal heterogeneity. Understanding these dynamics is crucial for tailoring transport properties like diffusion, viscosity and ionic conductivity. Molecular diffusion in DESs stems from transient caging and translation jumps, necessitating an understanding of how molecular structure regulates these processes. This study explores the influence of alkyl chain length on the nanoscopic dynamics of alkylamide-lithium perchlorate based DESs using quasielastic neutron scattering (QENS) and molecular dynamics (MD) simulations. QENS results show that, despite its shorter chain length and lighter mass, acetamide (ACM) exhibited the lowest mobility among the alkylamides, including propanamide (PRM) and butyramide (BUT). Detailed analysis of QENS data reveals that long-range jump diffusion is fastest in ACM and slowest in BUT, essentially due to their differences in molecular size, mass and also enhanced complexation in longer alkyl chain molecules. However, the localized dynamics follows an unusual trend, where PRM is the fastest and ACM is the slowest. Despite greater flexibility in BUT, the slower caged dynamics impedes its localized motion. These findings highlight the interplay between alkyl chain length and DES dynamics, emphasizing role of molecular structure in governing transport properties.