Solvation dynamics in a prototypical ionic liquid + dipolar aprotic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + acetonitrile

Solvation energies, rotation times, and 100 fs to 20 ns solvation response functions of the solute coumarin 153 (C153) in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Im41][BF4]) + acetonitrile (CH3CN) at room temperature (20.5 °C) are reported. Available density, shear viscosity, and electrical conductivity data at 25 °C are also collected and parametrized, and new data on refractive indices and component diffusion coefficients presented. Solvation free energies and reorganization energies associated with the S0 ↔ S1 transition of C153 are slightly (≤15%) larger in neat [Im41][BF4] than in CH3CN. No clear evidence for preferential solvation of C153 in these mixtures is found. Composition-dependent diffusion coefficients (D) of Im41+ and CH3CN as well as C153 rotation times (τ) are approximately related to solution viscosity (η) as D, τ ∝ ηp with values of p = −0.88, −0.77, and +0.90, respectively. Spectral/solvation response functions (Sν(t)) are bimodal at all compositions, consisting of a subpicosecond fast component followed by a broadly distributed slower component extending over ps-ns times. Integral solvation times (⟨τsolv⟩ = ∫0∞Sν(t) dt) follow a power law on viscosity for mixture compositions 0.2 ≤ xIL ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [J. Phys. Chem. B 2012, 116, 7509] as input, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture the distinctive bimodal character of the observed response. At xIL ∼ 1 predicted values of ⟨τsolv⟩ are smaller than those observed by a factor of 2–3, but the two become approximately equal at xIL = 0.2. Predictions of a recent semimolecular theory [ J. Phys. Chem. B 2011, 115, 4011] are less accurate, being uniformly slower than the observed solvation dynamics.

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry B, copyright © 2014 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jp412086t.”

Files

Metadata

Work Title Solvation dynamics in a prototypical ionic liquid + dipolar aprotic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + acetonitrile
Access
Open Access
Creators
  1. Min Liang
  2. Xin-Xing Zhang
  3. Anne Kaintz
  4. Nikolaus P. Ernsting
  5. Mark Maroncelli
Keyword
  1. Coumarin 153
  2. Dielectric continuum
  3. Self-diffusion
  4. Solute rotation
  5. Density
  6. Refractive index
  7. Viscosity
  8. Electrical conductivity
License In Copyright (Rights Reserved)
Work Type Article
Publisher
  1. Journal of Physical Chemistry B
Publication Date January 14, 2014
Publisher Identifier (DOI)
  1. https://doi.org/10.1021/jp412086t
Deposited February 27, 2025

Versions

Analytics

Collections

This resource is currently not in any collection.

Work History

Version 1
published

  • Created

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Solvation_Dynamics_in_a_Prototypical_Ionic_Liquid.pdf

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Creator Min Liang

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Creator Xin Xing Zhang

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Creator Anne Kaintz

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Creator Nikolaus P. Ernsting

    February 27, 2025 20:41 by Researcher Metadata Database

  • Added Creator Mark Maroncelli

    February 27, 2025 20:41 by Researcher Metadata Database

  • Published

    February 27, 2025 20:41 by Researcher Metadata Database

  • Updated

    February 27, 2025 21:04 by [unknown user]

  • Updated Keyword, Description Show Changes

    March 04, 2025 14:37 by avs5190

    Keyword
    • Coumarin 153, Dielectric continuum, Self-diffusion, Solute rotation, Density, Refractive index, Viscosity, Electrical conductivity
    Description
    • Solvation energies, rotation times, and 100 fs to 20 ns solvation response functions of the solute coumarin 153 (C153) in mixtures of 1-butyl-3- methylimidazolium tetrafluoroborate ([Im<sub>41</sub>][BF<sub>4</sub>]) + acetonitrile (CH<sub>3</sub>CN) at room temperature (20.5 C) are reported. Available density, shear viscosity, and electrical conductivity data at 25 C are also collected and parametrized, and new data on refractive indices and component diffusion coefficients presented. Solvation free energies and reorganization energies associated with the S<sub>0</sub> â" S <sub>1</sub> transition of C153 are slightly (≤15%) larger in neat [Im <sub>41</sub>][BF<sub>4</sub>] than in CH<sub>3</sub>CN. No clear evidence for preferential solvation of C153 in these mixtures is found. Composition-dependent diffusion coefficients (D) of Im<sub>41</sub><sup>+</sup> and CH<sub>3</sub>CN as well as C153 rotation times (τ) are approximately related to solution viscosity (η) as D, τ η<sup>p</sup> with values of p = -0.88, -0.77, and +0.90, respectively. Spectral/solvation response functions (S <sub>ν</sub>(t)) are bimodal at all compositions, consisting of a subpicosecond fast component followed by a broadly distributed slower component extending over ps-ns times. Integral solvation times (〈τ <sub>solv</sub>〉 = ∫0∞S<sub>ν</sub>(t) dt) follow a power law on viscosity for mixture compositions 0.2 ≤ x<sub>IL</sub> ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [ J. Phys. Chem. B 2012, 116, 7509 ] as input, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture the distinctive bimodal character of the observed response. At x<sub>IL</sub> ∼ 1 predicted values of 〈τ<sub>solv</sub>〉 are smaller than those observed by a factor of 2-3, but the two become approximately equal at x<sub>IL</sub> = 0.2. Predictions of a recent semimolecular theory [ J. Phys. Chem. B 2011, 115, 4011 ] are less accurate, being uniformly slower than the observed solvation dynamics.
    • Solvation energies, rotation times, and 100 fs to 20 ns solvation response functions of the solute coumarin 153 (C153) in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Im41][BF4]) + acetonitrile (CH3CN) at room temperature (20.5 °C) are reported. Available density, shear viscosity, and electrical conductivity data at 25 °C are also collected and parametrized, and new data on refractive indices and component diffusion coefficients presented. Solvation free energies and reorganization energies associated with the S0 ↔ S1 transition of C153 are slightly (≤15%) larger in neat [Im41][BF4] than in CH3CN. No clear evidence for preferential solvation of C153 in these mixtures is found. Composition-dependent diffusion coefficients (D) of Im41+ and CH3CN as well as C153 rotation times (τ) are approximately related to solution viscosity (η) as D, τ ∝ ηp with values of p = −0.88, −0.77, and +0.90, respectively. Spectral/solvation response functions (Sν(t)) are bimodal at all compositions, consisting of a subpicosecond fast component followed by a broadly distributed slower component extending over ps-ns times. Integral solvation times (⟨τsolv⟩ = ∫0∞Sν(t) dt) follow a power law on viscosity for mixture compositions 0.2 ≤ xIL ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [J. Phys. Chem. B 2012, 116, 7509] as input, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture the distinctive bimodal character of the observed response. At xIL ∼ 1 predicted values of ⟨τsolv⟩ are smaller than those observed by a factor of 2–3, but the two become approximately equal at xIL = 0.2. Predictions of a recent semimolecular theory [ J. Phys. Chem. B 2011, 115, 4011] are less accurate, being uniformly slower than the observed solvation dynamics.
  • Renamed Creator Xin-Xing Zhang Show Changes

    March 04, 2025 14:37 by avs5190

    • Xin Xing Zhang
    • Xin-Xing Zhang