Your browser doesn't support javascript.
loading
Solvation dynamics in a prototypical ionic liquid + dipolar aprotic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + acetonitrile.
Liang, Min; Zhang, Xin-Xing; Kaintz, Anne; Ernsting, Nikolaus P; Maroncelli, Mark.
Afiliación
  • Liang M; Departments of Chemistry, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
J Phys Chem B ; 118(5): 1340-52, 2014 Feb 06.
Article en En | MEDLINE | ID: mdl-24422509
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 ∝ η(p) 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 (⟨τ(solv)⟩ = ∫(0)(∞)Sν(t) dt) follow a power law on viscosity for mixturecompositions 0.2 ≤ x(IL) ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [J. Phys. Chem. B 2012, 116, 7509] asinput, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture thedistinctive bimodal character of the observed response. At x(IL) ∼ 1 predicted values of ⟨τ(solv)⟩ are smaller than those observed by a factor of 2-3, but the two become approximately equal at x(IL) = 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.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2014 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2014 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos