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Fluorescence spectroscopic studies of (acetamide + sodium/potassium thiocyanates) molten mixtures: Composition and temperature dependence
, H. Al Rasid Gazi, H.K. Kashyap, R. Biswas
Published in American Chemical Society
Volume: 114
Issue: 15
Pages: 5066 - 5081
Steady state and time-resolved fluorescence spectroscopic techniques have been used to explore the Stokes shift dynamics and rotational relaxation of a dipolar solute probe in molten mixtures of acetamide (CH3CONH 2) with sodium and potassium thiocyanates (Na /KSCN) at T ∼ 318 K and several other higher temperatures. The dipolar solute probe employed for this study is coumarin 153 (C153). Six different fractions (f) of KSCN of the following ternary mixture composition, 0.75CH3CONH2 + 0.25[(1 - f)NaSCN + fKSCN], have been considered. The estimated experimental dynamic Stokes shift for these systems ranges between 1800 and 2200 cm -1 (±250 cm-1), which is similar to what has been observed with the same solute probe in several imidazolium cation based room temperature ionic liquids (RTIL) and in pure amide solvents. Interestingly, this range of estimated Stokes shift, even though not corresponding to the megavalue of static dielectric constant reported in the literature for a binary mixture of molten CH3CONH2 and NaSCN, exhibits a nonmonotonic KSCN concentration dependence. The magnitudes of the dynamic Stokes shift detected in the present experiments are significantly less than the estimated ones, as nearly 40-60% of the total shift is missed due to the limited time resolution employed (full-width at half-maximum of the instrument response function ∼70 ps). The solvation response function, constructed from the detected shifts in these systems, exhibits triexponential decay with the fastest time constant (τ1) in the 10-20 ps range, which might be much shorter if measured with a better time resolution. The second time constant (τ2) lies in the 70-100 ps range, and the third one (τ3) ranges between 300 and 800 ps. Both these time constants (τ2 and τ3) show alkali metal ion concentration dependence and exhibit viscosity decoupling at higher viscosity in the NaSCN-enriched region. Time dependent rotational anisotropy has been found to be biexponential at all mixture compositions studied. Both the average solvation (〈τs〉) and rotation (〈τr〉) times of C153 in these mixtures exhibit fractional power law dependence on medium viscosity (〈τx〉 ∞ νp, x being solvation or rotation). For solvation, p is found to be 0.46, which is very different from that obtained for common polar and nonpolar solvents, and RTILs (p ≈ 1). For rotation, p ≈ 0.65, which is again different from the value (p ≈ 1) obtained for common polar solvents and RTILs but very similar to that (p ≈ 0.6) found for nonpolar solvents. In addition, experimentally measured average rotation times in these mixtures are found to exhibit slip behavior in the low ν/T region, which gradually transforms to subslip as ν/T increases. Calculations using a recently developed semimolecular theory predict a total dynamic Stokes shift for C153 (dipolar solute) in these molten mixtures near ∼1600 cm-1 where the solute-solvent (dipole-dipole) and the ion-solute (ion-dipole) interactions contribute respectively ∼80% and ∼20% to the calculated total shift. Like in experiments, the theoretically predicted solvation response function in the overdamped limit at each mixture composition has been found to be triexponential. The calculations in the underdamped limit, however, suggest a biphasic decay where a composition independent subpicosecond component and a much slower component with the time constant spreading over 150-850 ps contribute equally to constitute the total decay. The calculated average solvation times in this limit are found to be in better agreement with experimental results than the predictions from the overdamped limit. © 2010 American Chemical Society.
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