Solute rotation and solvation dynamics in an alcohol-functionalized room temperature ionic liquid

Steady-state and time-resolved fluorescence behaviors of two dipolar solutes, coumarin 153 and 4-aminophthalimide, have been studied in an alcohol-functionalized room-temperature ionic liquid, 1-(hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. The steady-state fluorescence parameters have been exploited for the estimation of the polarity of this ionic liquid and to obtain information on the hydrogen bonding interaction between the ionic liquid and the probe molecules. The time-resolved measurements have been focused on the dynamics of solvation by studying the dynamic Stokes shift in the ps-ns time scale and solute rotation by measuring the time dependence of the fluorescence anisotropy. The time-resolved anisotropy studies reveal a significant slow down of the rotational motion of one of the probe molecules. The time-dependent fluorescence Stokes shift measurements suggest that the time-resolvable part of the dynamics is biphasic in nature, highly dependent on the probe molecule and the ultrafast component is comparatively less than that in other ionic liquids. The influence of the hydrogen bonding interaction between the probe molecules and the ionic liquids on the solute rotation and the various components of the solvation dynamics is carefully analyzed in an attempt to obtain further insight into the mechanism of solvation in these novel media.     

Studies on the Solvation Dynamics of Coumarin 153 in 1‐Ethyl‐3‐Methylimidazolium Alkylsulfate Ionic Liquids: Dependence on Alkyl Chain Length

Steady‐state and time‐resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1‐ethyl‐3‐methylimidazolium alkylsulfate ([C₂mim][C_nOSO₃]) ionic liquids differing only in the length of the linear alkyl chain (n=4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady‐state absorption and emission maxima of C153 on going from the C₄OSO₃ to the C₈OSO₃ system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time‐zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes–Einstein–Debye (SED), Gierer–Wirtz (GW), and Dote–Kivelson–Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity.     

Exponential probe rotation in glass-forming liquids

Using time resolved optical depolarization, we have studied the rotational behavior of molecular probes in supercooled liquids near the glass transition temperature T(g). Simultaneously, the dynamics of the liquid immediately surrounding these rigid probes is measured by triplet state solvation experiments. This direct comparison of solute and solvent dynamics is particularly suited for assessing the origin of exponential orientational correlation functions of probe molecules embedded in liquids which exhibit highly nonexponential structural relaxation. Polarization angle dependent Stokes shift correlation functions demonstrate that probe rotation time and solvent response time are locally correlated quantities in the case of smaller probe molecules. Varying the size of both guest and host molecules shows that the size ratio determines the rotational behavior of the probes. The results are indicative of time averaging being at the origin of exponential rotation of probes whose rotational time constant is slower than solvent relaxation by a factor of 20 or more.     

Solvation dynamics and electric field relaxation in an imidazolium-PF6 ionic liquid: from room temperature to the glass transition

Time-resolved phosphorescence spectra and anisotropy of quinoxaline were measured in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-HFP), in its supercooled state near the glass-transition temperature. The solvation dynamics results are compared with the rotational motion of the probe and with the dielectric behavior of the neat ionic liquid. The dynamics in the viscous state are highly dispersive and show a super-Arrhenius temperature dependence, as typical for glass-forming materials. Combined with room-temperature results, solvation dynamics is observed to follow the structural relaxation times in terms of eta/T for more than 10 decades, from subnanoseconds at room temperature to seconds near the glass-transition temperature T(g). The dielectric modulus relaxation follows this trend only for temperatures T > 1.2T(g) and departs significantly from eta/T in the 1.1T(g) > T > T(g) range. This deviation is reminiscent of the enhanced translational diffusion or fractional Stokes-Einstein behavior observed in many fragile supercooled liquids. Because the electric field relaxation in BMIM-HFP includes dc conductivity, this correlation function involves translational motion and thus displays the effect of enhanced diffusivity. A microscopic model is required for rationalizing the decoupling of solvation dynamics from the longitudinal time scales and the limitation of this effect to the viscous regime with T < 1.2T(g).     

Solvation and rotational dynamics of coumarin 153 in ionic liquids: comparisons to conventional solvents

Steady-state and time-resolved emission spectroscopy with 25 ps resolution are used to measure equilibrium and dynamic aspects of the solvation of coumarin 153 (C153) in a diverse collection of 21 room-temperature ionic liquids. The ionic liquids studied here include several phosphonium and imidazolium liquids previously reported as well as 12 new ionic liquids that incorporate two homologous series of ammonium and pyrrolidinium cations. Steady-state absorption and emission spectra are used to extract solvation free energies and reorganization energies associated with the S0 <--> S1 transition of C153. These quantities, especially the solvation free energy, vary relatively little in ionic liquids compared to conventional solvents. Some correlation is found between these quantities and the mean separation between ions (or molar volume). Time-resolved anisotropies are used to observe solute rotation. Rotation times measured in ionic liquids correlate with solvent viscosity in much the same way that they do in conventional polar solvents. No special frictional coupling between the C153 and the ionic liquid solvents is indicated by these times. But, in contrast to what is observed in most low-viscosity conventional solvents, rotational correlation functions in ionic liquids are nonexponential. Time-resolved Stokes shift measurements are used to characterize solvation dynamics. The solvation response functions in ionic liquids are also nonexponential and can be reasonably represented by stretched-exponential functions of time. The solvation times observed are correlated with the solvent viscosity, and the much slower solvation in ionic liquids compared to dipolar solvents can be attributed to their much larger viscosities. Solvation times of the majority of ionic liquids studied appear to follow a single correlation with solvent viscosity. Only liquids incorporating the largest phosphonium cation appear to follow a distinctly different correlation.     

Fluorescence probing of temperature-dependent dynamics and friction in ionic liquid local environments

The solvation dynamics and local orientational friction for a series of four ionic liquids have been probed using coumarin 153 (C153) as a function of temperature. These ionic liquids are comprised of nonaromatic organic cations paired with a common anion, bis(trifluoromethylsulfonyl)imide (NTf(2)-). The specific liquids are as follows: N-methyl-tri-N-butylammonium NTf(2)- (N(1444)+/NTf(2)-), N-hexyl-tri-N-butylammonium NTf(2)- (N(6444)+/NTf(2)-), N-methyl-N-butylpyrrolidinium NTf(2)- (Pyrr(14)+/NTf(2)-), and N-methyl-N-ethoxyethylpyrrolidinium NTf(2)- (Pyrr(1(2O2))+/NTf(2)-). The observed solvation dynamics and fluorescence depolarization dynamics occur over a broad range of time scales that can only be adequately fit by functions including three or more exponential components. Stretched exponential distributions cannot adequately fit our data. The solvation and reorientational dynamics of the C153 probe are studied over a range of temperatures from 278.2 to 353.2 K. For both the solvation dynamics and the probe reorientational dynamics, the observed temperature dependence is well fit by a Vogel-Tammann-Fulcher law. To correlate the observed microscopic dynamics with macroscopic physical properties, temperature-dependent viscosities are also measured. Differential scanning calorimetry is used to study the thermodynamics of the phase transitions from the liquid to supercooled liquid to glassy states. For the two tetraalkylammonium liquids, the observed melting transitions occur near 300 K, so we are able to study the dynamics in a clearly supercooled regime. Very long time scale orientational relaxation time constants dynamics on the order of 100 ns are observed in the C153 fluorescence anisotropy. These are interpreted to arise from long-lived local structures in the environment surrounding the C153 probe.     

Characterization of the solvation dynamics of an ionic liquid via molecular dynamics simulation

The solvation dynamics of ionic liquids have been the subject of intense experimental study but remain poorly understood. We present the results of molecular dynamics simulations of the solvation dynamics of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate in response to photoexcitation of the fluorescent dye coumarin-153. We reproduce the time-resolved fluorescence Stokes shift using linear response theory, then use novel statistical techniques to analyze cation and anion contributions to the signal. We find that the solvation dynamics are dominated by collective ionic motion and characterize the time scale for various features of the collective response. Further, we use the Steele analysis [Mol. Phys. 61, 1031 (1987)] to characterize the contributions to the observed Stokes shift made by translational and rovibrational degrees of freedom. Our results indicate that in contrast to molecular liquids, the rovibrational response is trivial and the observed fluorescence response arises almost entirely from ionic translation. Our results resolve previously open questions in the literature about the nature of the rapid dynamics in room-temperature ionic liquids and offer insight into the physical principles governing ionic liquid behavior on longer time scales.     

Temperature dependence of anisotropy decay and solvation dynamics of coumarin 153 in gamma-cyclodextrin aggregates

Effect of temperature on the fluorescence anisotropy decay and the ultraslow component of solvation dynamics of coumarin 153 (C153) in a gamma-cyclodextrin (gamma-CD) nanocavity are studied using a picosecond set up. The steady-state anisotropy (0.13 +/- 0.01) and residual anisotropy (0.14 +/- 0.01) in fluorescence anisotropy decay in an aqueous solution containing 7 microM C153 and 40 mM gamma-CD are found to be quite large. This indicates formation of large linear nanotube aggregates of gamma-CD linked by C153. It is estimated that >53 gamma-CD units are present in each aggregate. In these aggregates with rise in temperature, the average solvation time ((obs)) decreases markedly from 680 ps at 278 K to 160 ps at 318 K. The dynamic Stokes shift is found to decrease from 800 cm(-1) at 278 K to 250 cm(-1) at 318 K. The fraction of dynamic Stokes shift (f(d)) detected in a picosecond set up is calculated using the Fee-Maroncelli procedure. The corrected solvation time ((corr) = f(d)<(tau(s)>(obs)) displays an Arrhenius type temperature dependence. From the temperature variation, the activation energy and entropy of the solvation process are determined to be 12.5 kcal M(-1) and 28 cal M(-1) K(-1), respectively. The ultraslow component and its temperature dependence are ascribed to a dynamic exchange between bound and free water molecules.     

Edge excitation red shift and energy migration in quinine bisulphate dication

Photoinduced excited state dynamical processes in quinine sulphate dication (QSD) have been studied over a wide range of solute concentrations using steady state and nanosecond time-resolved fluorescence spectroscopic techniques. The edge excitation red shift (EERS) of emission maximum, emission wavelength dependence of fluorescence lifetimes and the time dependence of emission maximum are known to occur due to the solvent relaxation process. With increase in solute concentration, the emission spectrum shifts towards the lower frequencies accompanied with decrease in fluorescence intensity, however, absorption spectrum remains unchanged. A decrease in EERS, fluorescence lifetimes, time dependent fluorescence Stokes shift (TDFSS), fluorescence polarization and the solvent relaxation time (τ_r) is observed with the increase in solute concentration. The process of energy migration among the QSD ions along with solvent relaxation has been found responsible for the above experimental findings.     

Ultrafast solvation dynamics of coumarin 153 in imidazolium-based ionic liquids

The dynamic Stokes shift of coumarin 153 has been measured in two room-temperature ionic liquids, 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-propyl-3-methylimidazolium tetrafluoroborate, using the fluorescence up-conversion technique with a 230 fs instrumental response function. A component of about 10-15% of the total solvation shift is found to take place on an ultrafast time scale < 10 ps. The amplitude of this component is substantially less than assumed previously by other authors. The origin of the difference in findings could be partly due to chromophore-internal conformational changes on the ultrafast time scale, superimposed to solvation-relaxation, or due to conformational changes of the chromophore ground state in polar and apolar environments. First three-pulse photon-echo peak-shift experiments on indocyanine green in room-temperature ionic liquids and in ethanol indicate a difference in the inertial component of the early solvent relaxation of <100 fs.     

Temperature dependence of solvation dynamics of probe molecules in methanol-doped ice and in liquid ethanol

We have studied the solvation statics and dynamics of coumarin 343 and a strong photoacid (pK* approximately 0.7) 2-naphthol-6, 8-disulfonate (2N68DS) in methanol-doped ice (1% molar concentration of methanol) and in cold liquid ethanol in the temperature range of 160-270 K. Both probe molecules show a relatively fast solvation dynamics in ice, ranging from a few tens of picoseconds at about 240 K to nanoseconds at about 160 K. At about 160 K in doped ice, we observe a sharp decrease of the dynamic Stokes shift of both coumarin 343 and 2N68DS. Its value is approximately only 200 cm-1 at approximately 160 K compared to about 1100 cm-1 at T >/= 200 K (at times longer than t > 10 ps). We find a good correlation between the inefficient and slow excited-state proton-transfer rate at low-temperature ice, T < 180 K, and the dramatic decrease of the solvation energy, as measured by the dynamic band shift, at these low temperatures. We find that the average solvation rate in ice is similar to its value in liquid ethanol at all given temperatures in the range of 200-250 K. The surprisingly fast solvation rate in ice is explained by the relatively large freedom of the water hydrogen rotation in ice Ih.     

Free volume in imidazolium triflimide ([C3MIM][NTf2]) ionic liquid from positron lifetime: amorphous, crystalline, and liquid states

Positron annihilation lifetime spectroscopy (PALS) is used to study the ionic liquid 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide [C(3)MIM][NTf(2)] in the temperature range between 150 and 320 K. The positron decay spectra are analyzed using the routine LifeTime-9.0 and the size distribution of local free volumes (subnanometer-size holes) is calculated. This distribution is in good agreement with Fürth's classical hole theory of liquids when taking into account Fürth's hole coalescence hypothesis. During cooling, the liquid sample remains in a supercooled, amorphous state and shows the glass transition in the ortho-positronium (o-Ps) lifetime at 187 K. The mean hole volume varies between 70 ?(3) at 150 K and 250 ?(3) at 265-300 K. From a comparison with the macroscopic volume, the hole density is estimated to be constant at 0.20×10(21) g(-1) corresponding to 0.30 nm(-3) at 265 K. The hole free volume fraction varies from 0.023 at 185 K to 0.073 at T(m)+12 K=265 K and can be estimated to be 0.17 at 430 K. It is shown that the viscosity follows perfectly the Cohen-Turnbull free volume theory when using the free volume determined here. The heating run clearly shows crystallization at 200 K by an abrupt decrease in the mean <τ(3)> and standard deviation σ(3) of the o-Ps lifetime distribution and an increase in the o-Ps intensity I(3). The parameters of the second lifetime component <τ(2)> and σ(2) behave parallel to the o-Ps parameters, which also shows the positron's (e(+)) response to structural changes. During melting at 253 K, all lifetime parameters recover to the initial values of the liquid. An abrupt decrease in I(3) is attributed to the solvation of e(-) and e(+) particles. Different possible interpretations of the o-Ps lifetime in the crystalline state are briefly discussed.     

Fluorescence studies in a pyrrolidinium ionic liquid: polarity of the medium and solvation dynamics

While the imidazolium ionic liquids have been studied for some time, little is known about the pyrrolidinium ionic liquids. In this work, steady-state and picosecond time-resolved fluorescence behavior of three electron donor-acceptor molecules, coumarin-153 (C153), 4-aminophthalimide (AP), and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), has been studied in a pyrrolidinium ionic liquid, N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, abbreviated here as [bmpy][Tf2N]. The steady-state fluorescence data of the systems suggest that the microenvironment around these probe molecules, which is measured in terms of the solvent polarity parameter, E(T)(30), is similar to that in 1-decanol and that the polarity of this ionic liquid is comparable to that of the imidazolium ionic liquids. All three systems exhibit wavelength-dependent fluorescence decay behavior, and the time-resolved fluorescence spectra show a progressive shift of the fluorescence maximum toward the longer wavelength with time. This behavior is attributed to solvent-mediated relaxation of the fluorescent state of these systems. The dynamics of solvation, which is studied from the time-dependent shift of the fluorescence spectra, suggests that approximately 45% of the relaxation is too rapid to be measured in the present setup having a time resolution of 25 ps. The remaining observable components of the dynamics consist of a short component of 115-440 ps (with smaller amplitude) and a long component of 610-1395 ps (with higher amplitude). The average solvation time is consistent with the viscosity of this ionic liquid. The dynamics of solvation is dependent on the probe molecule, and nearly 2-fold variation of the solvation time depending on the probe molecule could be observed. No correlation of the solvation time with the probe molecule could, however, be observed.     

Effect of ionic surfactants on the hydration behavior of triblock copolymer micelles: a solvation dynamics study of coumarin 153

Dynamic fluorescence Stokes shift measurements of coumarin 153 (C153) have been carried out to study the influence of ionic surfactants (sodium dodecyl sulfate, SDS and hexadecyltrimethylammonium chloride, CTAC) on the hydration behavior of aqueous poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)20 (P123) block copolymer micelles. Increase in SDS or CTAC concentration at a fixed P123 concentration induces the steady-state emission spectra of C153 to shift gradually toward lower energy. This is attributed to an increase in polarity (due to enhanced hydration) experienced by the probe as a consequence of incorporation of ionic head groups in the Corona region. The observed dynamic fluorescence Stokes shift value decreases more in mixed micellar systems than in pure copolymer micelles and the trends are quite similar in the presence of SDS and CTAC. The spectral shift correlation functions were observed to be nonexponential in nature. Critical analysis of the spectral shift correlation function indicates a fast solvation component (<0.2 ns) in P123 micelles, which was absent in the presence of ionic surfactants. Due to increased hydration in the presence of ionic surfactants, the initial fast solvation event was elusive in mixed copolymer-surfactant systems, reflecting the absence of faster solvation component and reduced observed Stokes shift in mixed systems. It has been argued that in the low surfactant concentration region, increase in hydration with the incorporation of ionic head groups in the Corona region is mainly due to increase in mechanically trapped water content. However, at higher surfactant concentrations, bound water content dominates and leads to slower solvation dynamics. The present results also indicate that though CTAC alters the Corona hydration more efficiently than SDS, the overall influence of ionic surfactants on the Corona hydration is grossly similar irrespective of the cationic or anionic nature of the surfactants. Interaction of SDS and CTAC with poly(ethylene oxide)(100)-poly(propylene oxide)(70)-poly(ethylene oxide)(100) (F127) block copolymer micelles has also been studied to comprehend the effect of copolymer composition. The overall trends in dynamic fluorescence Stokes shift and solvation times are similar in both the copolymer micelles.     

The Effect of Pre-solvation in the Ground State on Photoinduced Electron Transfer in Ionic Liquids

Photoinduced intramolecular charge transfer (CT) dynamics of the asymmetric and symmetric molecules, 4-(9-anthryl)-N,N-dimethylaniline (ADMA) and 9,9′-bianthryl (BA), was investigated by means of time-resolved fluorescence (TRF) spectroscopy and compared with the solvation dynamics of coumarin 153 (C153) in several ionic liquids (ILs). The normalized dynamic Stokes shift (DSS) function for the CT state emission of ADMA in the sub-ns to ns time scale is almost the same as those of BA and C153 in most of the ILs studied, in spite of the much larger Stokes shift of ADMA compared to those of BA and C153. On the other hand, the contribution from ultrafast DSS within 30 ps, which was undetectable with the time resolution in the present study, was estimated to be smaller for BA than that for ADMA. Meanwhile, in phosphonium IL, the DSS in sub-ns to ns time range was solute dependent. This peculiarity in phosphonium IL is discussed from the viewpoint of the hierarchy of the solvation dynamics.     

Measurements of the complete solvation response in ionic liquids

Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4'-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25 degrees C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.     

Measurement of solvation responses at multiple sites in a globular protein

Proteins respond to electrostatic perturbations through complex reorganizations of their charged and polar groups, as well as those of the surrounding media. These solvation responses occur both in the protein interior and on its surface, though the exact mechanisms of solvation are not well understood, in part because of limited data on the solvation responses for any given protein. Here, we characterize the solvation kinetics at sites throughout the sequence of a small globular protein, the B1 domain of streptococcal protein G (GB1), using the synthetic fluorescent amino acid Aladan. Aladan was incorporated into seven different GB1 sites, and the time-dependent Stokes shift was measured over the femtosecond to nanosecond time scales by fluorescence upconversion and time-correlated single photon counting. The seven sites range from buried within the protein core to fully solvent-exposed on the protein surface, and are located on different protein secondary structures including beta-sheets, helices, and loops. The dynamics in the protein sites were compared against the free fluorophore in buffer. All protein sites exhibited an initial, ultrafast Stokes shift on the subpicosecond time scale similar to that observed for the free fluorophore, but smaller in magnitude. As the probe is moved from the surface to more buried sites, the dynamics of the solvation response become slower, while no clear correlation between dynamics and secondary structure is observed. We suggest that restricted movements of the surrounding protein residues give rise to the observed long time dynamics and that such movements comprise a large portion of the protein's solvation response. The proper treatment of dynamic Stokes shift data when the time scale for solvation is comparable to the fluorescence lifetime is discussed.     

Dynamic processes in a silicate liquid from above melting to below the glass transition

We collect and critically analyze extensive literature data, including our own, on three important kinetic processes--viscous flow, crystal nucleation, and growth--in lithium disilicate (Li(2)O·2SiO(2)) over a wide temperature range, from above T(m) to 0.98T(g) where T(g) ≈ 727 K is the calorimetric glass transition temperature and T(m) = 1307 K, which is the melting point. We found that crystal growth mediated by screw dislocations is the most likely growth mechanism in this system. We then calculated the diffusion coefficients controlling crystal growth, D(eff)(U), and completed the analyses by looking at the ionic diffusion coefficients of Li(+1), O(2-), and Si(4+) estimated from experiments and molecular dynamic simulations. These values were then employed to estimate the effective volume diffusion coefficients, D(eff)(V), resulting from their combination within a hypothetical Li(2)Si(2)O(5) "molecule". The similarity of the temperature dependencies of 1/η, where η is shear viscosity, and D(eff)(V) corroborates the validity of the Stokes-Einstein/Eyring equation (SEE) at high temperatures around T(m). Using the equality of D(eff)(V) and D(eff)(η), we estimated the jump distance λ ~ 2.70 ? from the SEE equation and showed that the values of D(eff)(U) have the same temperature dependence but exceed D(eff)(η) by about eightfold. The difference between D(eff)(η) and D(eff)(U) indicates that the former determines the process of mass transport in the bulk whereas the latter relates to the mobility of the structural units on the crystal/liquid interface. We then employed the values of η(T) reduced by eightfold to calculate the growth rates U(T). The resultant U(T) curve is consistent with experimental data until the temperature decreases to a decoupling temperature T(d)(U) ≈ 1.1-1.2T(g), when D(eff)(η) begins decrease with decreasing temperature faster than D(eff)(U). A similar decoupling occurs between D(eff)(η) and D(eff)(τ) (estimated from nucleation time-lags) but at a lower temperatureT(d)(τ) ≈ T(g). For T > T(g) the values of D(eff)(τ) exceed D(eff)(η) only by twofold. The different behaviors of D(eff)(τ)(T) and D(eff)(U)(T) are likely caused by differences in the mechanisms of critical nuclei formation. Therefore, we have shown that at low undercoolings, viscosity data can be employed for quantitative analyses of crystal growth rates, but in the deeply supercooled liquid state, mass transport for crystal nucleation and growth are not controlled by viscosity. The origin of decoupling is assigned to spatially dynamic heterogeneity in glass-forming melts.     

Characterization of a Novel Intrinsic Luminescent Room‐Temperature Ionic Liquid Based on [P6,6,6,14][ANS]

Intrinsically luminescent room‐temperature ionic liquids (RTILs) can be prepared by combining a luminescent anion (more common) or cation with appropriate counter ions, rendering new luminescent soft materials. These RTILs are still new, and many of their photochemical properties are not well known. A novel intrinsic luminescent RTIL based on the 8‐anilinonaphthalene‐1‐sulfonate ([ANS]) anion combined with the trihexyltetradecylphosphonium ([P_6,6,6,14]) cation was prepared and characterized by spectroscopic techniques. Detailed photophysical studies highlight the influence of the ionic liquid environment on the ANS fluorescence, which together with rheological and ¹H NMR experiments illustrate the effects of both the viscosity and electrostatic interactions between the ions. This material is liquid at room temperature and possesses a glass transition temperature (T_g) of 230.4 K. The fluorescence is not highly sensitive to factors such as temperature, but owing to its high viscosity, dynamic Stokes shift measurements reveal very slow components for the IL relaxation.     

NMR chemical shifts of xenon in mixed aprotic solvents: A probe of liquid structure

The chemical shift of elemental xenon is extremely sensitive to the environment. In aprotic solvents, the presence of xenon has little effect on the solvent structure, and preferential solvation is not observed in any mixed solvent system. Consequently, xenon shifts can reveal the presence of short range order in certain liquids. Chemical shift data are presented for several model systems, including mixtures of different alkanes, alkanes with benzene, alkanes with acetone, and carbon tetrachloride with dimethylformamide (DMF). In certain cases, the xenon shift is strongly non-linear with composition. This effect arises from a specific interaction between the two solvents in the CCl₄-DMF system, while it reflects short range liquid order in the acetone-alkane systems. This effect is also apparent in the deviation of the densities of the acetone-alkane mixtures from ideality.