Intermolecular Vibrational and Orientational Dynamics of Deep Eutectic Solvents Composed of Lithium Bis(trifluoromethylsulfonyl)amide and Organic Amides Revealed by Dynamic Kerr Effect Spectroscopy DOI

Maharoof Koyakkat,

Hideaki Shirota

The Journal of Physical Chemistry B, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

In this study, we investigated the intermolecular dynamics, including vibration and orientational of five deep eutectic solvents (DESs) consisting lithium bis(trifluoromethylsulfonyl)amide organic amides, such as acetamide, propanamide, N-methylacetamide, butyramide, urea, at a mole ratio 1:3 using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) subpicosecond optical (ps-OKES). The fs-RIKES results showed that line shape low-frequency band N-methylacetamide was trapezoidal, while other amide-based DESs bimodal. peak first moment vibrational appearing in frequency range less than 250 cm-1 for acetamide- urea-based were higher-frequency region compared to three DESs, indicating stronger interactions. Furthermore, analysis intramolecular bands anion population transoid conformer slightly higher DES suggesting urea solvate cations more amides. slow relaxation dynamics all captured up 1 ns ps-OKES. also depended on amide species. However, time constant did not show clear correlation with viscosity; therefore, follow Stokes-Einstein-Debye hydrodynamic model. densities, viscosities, surface tensions, electrical conductivities measured comparison spectroscopic results.

Language: Английский

Correlating Viscosity Trends and Ultrafast Structural Dynamics in TMSO–Water and SFL–Water Binary Mixtures DOI

Jiman He,

Min Lin, Yuting Gao

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3544 - 3552

Published: March 31, 2025

The hydrogen bonding dynamics in tetramethylene sulfoxide (TMSO)-water and sulfolane (SFL)-water binary mixtures were investigated by using FTIR spectroscopy, ultrafast IR molecular (MD) simulations. Despite TMSO SFL sharing a similar cyclic backbone, markedly different viscosity behaviors observed. By employing SCN- as local probe, its distinct reorientational was observed that directly correlates with the contrasting trends two systems. In TMSO-water solutions, strong solute-water dominates water-water interactions, leading to maximum at intermediate concentrations. Conversely, of water molecules SFL-water solutions is decoupled from bulk due weaker interactions. MD simulations further elucidate how interplay between governs trends. This work advances our understanding complex aqueous environments provides systematic approach for connecting molecular-level interactions macroscopic fluid properties.

Language: Английский

Citations

0
Intermolecular Vibrational and Orientational Dynamics of Deep Eutectic Solvents Composed of Lithium Bis(trifluoromethylsulfonyl)amide and Organic Amides Revealed by Dynamic Kerr Effect Spectroscopy DOI

Maharoof Koyakkat,

Hideaki Shirota

The Journal of Physical Chemistry B, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

In this study, we investigated the intermolecular dynamics, including vibration and orientational of five deep eutectic solvents (DESs) consisting lithium bis(trifluoromethylsulfonyl)amide organic amides, such as acetamide, propanamide, N-methylacetamide, butyramide, urea, at a mole ratio 1:3 using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) subpicosecond optical (ps-OKES). The fs-RIKES results showed that line shape low-frequency band N-methylacetamide was trapezoidal, while other amide-based DESs bimodal. peak first moment vibrational appearing in frequency range less than 250 cm-1 for acetamide- urea-based were higher-frequency region compared to three DESs, indicating stronger interactions. Furthermore, analysis intramolecular bands anion population transoid conformer slightly higher DES suggesting urea solvate cations more amides. slow relaxation dynamics all captured up 1 ns ps-OKES. also depended on amide species. However, time constant did not show clear correlation with viscosity; therefore, follow Stokes-Einstein-Debye hydrodynamic model. densities, viscosities, surface tensions, electrical conductivities measured comparison spectroscopic results.

Language: Английский

Citations

0