1. Unraveling relationship between complex lifetimes and microscopic diffusion in deep eutectic solvents.
- Author
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Rinesh, T., Srinivasan, H., Sharma, V. K., and Mitra, S.
- Subjects
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RELAXATION phenomena , *LITHIUM perchlorate , *HYDROGEN bonding , *SOLVENTS , *DIFFUSION kinetics , *DIFFUSION - Abstract
Aqueous mixtures of deep eutectic solvents (DESs) have emerged as a subject of interest in recent years for their tailored physicochemical properties. However, a comprehensive understanding of water's multifaceted influence on the microscopic dynamics, including its impact on improved transport properties of the DES, remains elusive. Additionally, the diffusion mechanisms within DESs manifest heterogeneous behavior, intricately tied to the formation and dissociation kinetics of complexes and hydrogen bonds. Therefore, it is imperative to explore the intricate interplay between bond kinetics, diffusion mechanism, and dynamical heterogeneity. This work employs water as an agent to explore their relationships by studying various relaxation phenomena in a DES based on acetamide and lithium perchlorate over a wide range of water concentrations. Notably, acetamide exhibits Fickian yet non-Gaussian diffusion across all water concentrations with Fickian ( τ f ) and Gaussian ( τ g ) timescales following a power-law relationship, τ g ∝ τ f γ , γ ∼ 1.4. The strength of coupling between bond kinetics and different diffusion timescales is estimated through various power-law relationships. Notably, acetamide–water hydrogen bond lifetime is linked to diffusive timescales through a single power-law over the entire water concentration studied. However, the relationship between diffusive timescales and the lifetime of acetamide–lithium complexes shows a sharp transition in behavior at 20 wt. % water, reflecting a change from vehicular diffusion below this concentration to structural diffusion above it. Our findings emphasize the critical importance of understanding bond dynamics within DESs, as they closely correlate with and regulate the molecular diffusion processes within these systems. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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