Femtosecond solvation dynamics in a neat ionic liquid and ionic liquid microemulsion: excitation wavelength dependence

Solvation dynamics in a neat ionic liquid, 1-pentyl-3-methyl-imidazolium tetra-flouroborate ([pmim][BF4]) and its microemulsion in Triton X-100 (TX-100)/benzene is studied using femtosecond up-conversion. In both the neat ionic liquid and the microemulsion, the solvation dynamics is found to depend on excitation wavelength (lambda(ex)). The lambda(ex) dependence is attributed to structural heterogeneity in neat ionic liquid (IL) and in IL microemulsion. In neat IL, the heterogeneity arises from clustering of the pentyl groups which are surrounded by a network of cation and anions. Such a nanostructural organization is predicted in many recent simulations and observed recently in an X-ray diffraction study. In an IL microemulsion, the surfactant (TX-100) molecules aggregate in form of a nonpolar peripheral shell around the polar pool of IL. The micro-environment in such an assembly varies drastically over a short distance. The dynamic solvent shift (and average solvation time) in neat IL as well as in IL microemulsions decreases markedly as lambda(ex) increases from 375 to 435 nm. In a [pmim][BF4]/water/TX-100/benzene quaternary microemulsion, the solvation dynamics is slower than that in a microemulsion without water. This is ascribed to the smaller size of the water containing microemulsion. The anisotropy decay in an IL microemulsion is found to be faster than that in neat IL.     

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.     

Ultrafast dynamics of pyrrolidinium cation ionic liquids

We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.     

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.     

Limiting ionic conductivity and solvation dynamics in formamide

A self-consistent microscopic theory has been used to calculate the limiting ionic conductivity of unipositive rigid ions in formamide at different temperatures. The calculated results are found to be in good agreement with the experimental data. The above theory can also predict successfully the experimentally observed temperature dependence of total ionic conductivity of a given uniunivalent electrolyte in formamide. The effects of dynamic polar solvent response on ionic conductivity have been investigated by studying the time dependent progress of solvation of a polarity probe dissolved in formamide. The intermolecular vibration (libration) band that is often detected in the range of 100-200 cm(-1) in formamide is found to play an important role in determining both the conductivity and the ultrafast polar solvent response in formamide. The time dependent decay of polar solvation energy in formamide has been studied at three different temperatures, namely, at 283.15, 298.15, and 328.15 K. While the predicted decay at 298.15 K is in good agreement with the available experimental data, the calculated results at the other two temperatures should be tested against experiments.     

Effect of nonpolar solvents on the solute rotation and solvation dynamics in an imidazolium ionic liquid

Recognizing the potential of the mixed solvent systems comprising ionic liquid as one of the constituents in real applications, the steady-state and time-resolved fluorescence behavior of C153 has been studied in neat 1-butyl-3-methylimidazolium hexafluorophosphate and its mixtures with nonpolar solvents, namely, toluene and 1,4-dioxane. No significant effect of the cosolvent on the steady-state absorption or fluorescence spectra of C153 in ionic liquid has been observed. Time-resolved fluorescence anisotropy measurements show a decrease of the rotational correlation time of C153 with gradual addition of the cosolvent. Solvation dynamics in ionic liquid-cosolvent mixtures is found to be biphasic, and a decrease of the average solvation time is observed with increasing amount of the cosolvent in solution. The time-zero spectrum of C153 is found to shift toward higher energy with gradual addition of the nonpolar solvent, suggesting that the probe molecule experiences a more nonpolar environment at the early stage of the dynamics in mixed solvents. The blue shift of the time-zero spectrum caused by the addition of the nonpolar solvent results in a larger Stokes shift of the time-dependent spectra due to solvent relaxation in mixed solvents. A comparison of the time-dependent spectral data of the ionic liquid-toluene and ionic liquid-dioxane systems shows that, while a small amount of toluene can significantly affect the dynamics, comparatively, a larger amount of dioxane is required to bring about the same effect. This is explained in terms of favorable interactions between toluene and the imidazolium ring system leading to a more effective solubilization of toluene in the cybotactic region of the probe.     

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.     

Dipolar solvation dynamics in room temperature ionic liquids: an effective medium calculation using dielectric relaxation data

Solvation dynamics in four imidazolium cation based room temperature ionic liquids (RTIL) have been calculated by using the recently measured dielectric relaxation data [ J. Phys. Chem. B 2008, 112, 4854 ] as an input in a molecular hydrodynamic theory developed earlier for studying solvation energy relaxation in polar solvents. Coumarin 153 (C153), 4-aminophthalimide (4-AP), and trans-4-dimethylamino-4'-cyanostilbene (DCS) have been used as probe molecules for this purpose. The medium response to a laser-excited probe molecule in an ionic liquid is approximated by that in an effective dipolar medium. The calculated decays of the solvent response function for these RTILs have been found to be biphasic and the decay time constants agree well with the available experimental and computer simulation results. Also, no probe dependence has been found for the average solvation times in these ionic liquids. In addition, dipolar solvation dynamics have been predicted for two other RTILs for which experimental results are not available yet. These predictions should be tested against experiments and/or simulation studies.     

Glucose solvation by the ionic liquid 1,3-dimethylimidazolium chloride: a simulation study

Simulations of beta-glucose in the ionic liquid 1,3-dimethylimidazolium chloride have been performed in order to examine the solvation environment of the carbohydrate. Both single molecule and 1:5 glucose:ionic liquid (16.7 wt %) solutions are studied, and the hydrogen bonding between sugar and solvent is examined. The primary solvation shell around the perimeter of the glucose ring consists predominantly of chloride anions which hydrogen bond to the hydroxyl groups. A small presence of the cation is also found, with the association occurring through the weakly acidic hydrogen at the 2-position of the imidazolium ring interacting with the oxygen atoms of the sugar secondary hydroxyls. An average chloride coordination number of 4 is found around the glucose for both the single molecule and high concentration simulations, despite the reduced chloride:glucose ratio in the latter case. In relation to the cation, the glucose molecules occupy positions above and below the plane of the imidazolium ring. Importantly, even at high glucose concentrations, no significant change in the anion-cation interactions and overall liquid structure of the ionic liquid is found, indicating that the glucose is readily accommodated by the solvent at this concentration. Dominant contributions to the sugar-ionic liquid interaction energy come from favorable hydrogen bonding (electrostatic) interactions between hydroxyls and chlorides, although a small favorable van der Waals energy contribution is also seen between the sugar and cations suggesting that the cation could be tailored in order to further improve the dissolution of glucose/cellulose in ionic liquid systems.     

Novel functionalized ionic liquid with a sulfur atom in the aliphatic side chain of the pyrrolidinium cation

A novel ionic liquid, never reported in literature until now, was properly designed, synthesized and preliminary investigated. This material was prepared combining the N-methylpyrrolidinium cation (PYR_1(2S1))⁺, exhibiting a sulfur atom in the alkyl side chain, with the bis(trifluoromethanesulfonyl)imide anion, (TFSI)⁻, to be addressed as safer electrolyte component for sulfur-based battery systems. The presence of sulfur within the cation side chain was found to prevent the crystallization of the ionic liquid even in the presence of lithium salt. Cyclic voltammetries have clearly indicated that Li⁺ cation exhibits good mobility and is reversibly plated/stripped in PYR_1(2S1)TFSI–LiTFSI electrolytes with high efficiency.     

Bandwidth analysis of solvation dynamics in a simple liquid mixture

The time-dependent energy distribution of solvation dynamics is studied by molecular dynamics simulations of a Lennard-Jones mixture. We calculate the response functions of the average and the variance which correspond to the spectral peak shift and bandwidth. Our calculation shows that the variance relaxation is slower than that of the average. The result agrees qualitatively with the experimental results. Dividing the obtained response functions into subcomponents caused by each solvent, we find that the relaxation is dominated by that solvent which strongly interacts with the solute. Extracting the redistribution component from the response functions, we find that it causes the slower relaxation of the response function. Thus, we conclude that the difference of the slower relaxations between the average and variance is caused by the redistribution process.     

Vibrational relaxation of liquid water in ionic solvation shells

Femtosecond two-color pump–probe spectroscopy is used to measure the vibrational lifetime of the O–H stretch vibration in solutions of KF, NaCl, NaBr, and NaI in HDO:D₂O. We observe a slow component (roughly 2–4 times slower than in HDO:D₂O) in the decay of the absorption change, which is due to O–H groups that are hydrogen bonded to the dissolved anions. The time constant of this slow component depends on the nature of the anions and is observed to decrease with temperature, in contrast with the temperature dependence of the relaxation of the OH stretch vibration in pure HDO:D₂O.     

Ionic and dipolar solvation dynamics in liquid water

The solvation time correlation function for solvation in liquid water was measured recently. The solvation was found to be very fast, with a time constant equal to 55 fs. In this article we present theoretical studies on solvation dynamics of ionic and dipolar solutes in liquid water, based on the molecular hydrodynamic approach developed earlier. The molecular hydrodynamic theory can successfully predict the ultrafast dynamics of solvation in liquid water as observed from recent experiments. The present study also reveals some interesting aspects of dipolar solvation dynamics, which differs significantly from that of ionic solvation. Dedicated to Prof. C N R Rao on his 60th birthday     

Fluorescence anisotropy decay and solvation dynamics in a nanocavity: coumarin 153 in methyl beta-cyclodextrins

Fluorescence anisotropy decay and solvation dynamics of coumarin 153 (C153) are studied in dimethyl beta-cyclodextrin (DIMEB) and trimethyl beta-cyclodextrin (TRIMEB) nanocavity in water. C153 binds to DIMEB and TRIMEB to form both 1:1 and 1:2 (C153:cyclodextrin) complexes. The anisotropy decays of C153 in DIMEB and TRIMEB are found to be biexponential. The fast component of anisotropy decay (approximately 1000 ps) is attributed to the 1:1 complex and the slower one (approximately 2500 ps) to the 1:2 complex. From the components of the anisotropy decay, the length of the 1:1 and 1:2 complexes are estimated. Solvation dynamics of C153 in DIMEB exhibits a very fast (2.4 ps) component (41%) and two slower components of 50 ps (29%) and 1450 ps (30%). Solvation dynamics in TRIMEB is described by three slow components of 10.3 ps (24%), 240 ps (45%), and 2450 ps (31%). Possible origins of the ultraslow components are discussed.     

Femto- and picosecond fluorescence studies of solvation and non-radiative deactivation of ionic styryl dyes in liquid solution

A comparative study of the solvation and non-radiative relaxation dynamics of bridged and unbridged ionic styryl dye compounds is reported. Femto- and picosecond fluorescence transient measurements reveal solvation dynamics on a picosecond timescale of the solutes in ethanol, benzonitrile and decanol. Bridging is found to strongly affect the lifetime of the emissive state. It is shown that the presence of unbridged styryl-group single bonds allows for an effective non-radiative decay process. This decay process is suppressed by double chemical bridging.     

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.