Intermolecular vibrations and diffusive orientational dynamics of Cs condensed ring aromatic molecular liquids

The ultrafast dynamics, including the intermolecular vibrations and the diffusive orientational dynamics, of the neat C(s) symmetry condensed ring aromatic molecular liquids benzofuran, 1-fluoronaphtalene, and quinoline were investigated for the first time by means of femtosecond Raman-induced Kerr effect spectroscopy. To understand the features of these C(s) condensed ring aromatic molecular liquids, reference singular aromatic molecular liquids, furan, fluorobenzene, pyridine, and benzene, were also studied. High quality low-frequency Kerr spectra of the aromatic molecular liquids were obtained by Fourier-transform deconvolution analysis of the measured Kerr transients. The Kerr spectra of the C(s) condensed ring aromatic molecular liquids are bimodal, as are those of the reference singular aromatic molecular liquids. The first moment of the intermolecular vibrational spectrum and the peak frequencies of the high- and low-frequency components in the broad spectrum band were compared with their molecular properties such as the rotational constants, molecular weight, and intermolecular (bimolecular) force. The comparisons show that the molecular volume (related to molecular weight and rotational constants) is a dominant property for the characteristic frequency of the entire intermolecular vibrational spectrum. The observed intramolecular vibrational modes in the Kerr spectra of the aromatic molecular liquids were also assigned on the basis of the ab initio quantum chemical calculation results. In their picosecond diffusive orientational dynamics, the slowest relaxation time constant for both the condensed ring and singular aromatic molecular liquids can be accounted for by the simple Stokes-Einstein-Debye hydrodynamic model.     

A new ultrafast technique for measuring the terahertz dynamics of chiral molecules: the theory of optical heterodyne-detected Raman-induced Kerr optical activity

Optical heterodyne-detected Raman-induced Kerr optical activity (OHD-RIKOA) is a nonresonant ultrafast chiroptical technique for measuring the terahertz-frequency Raman spectrum of chirally active modes in liquids, solutions, and glasses of chiral molecules. OHD-RIKOA has the potential to provide much more information on the structure of molecules and the symmetries of librational and vibrational modes than the well-known nonchirally sensitive technique optical heterodyne-detected Raman-induced Kerr-effect spectroscopy (OHD-RIKES). The theory of OHD-RIKOA is presented and possible practical ways of performing the experiments are analyzed.     

Comparative study of temperature dependent orientational relaxation in a model thermotropic liquid crystal and in a model supercooled liquid

Recent optical Kerr effect experiments have revealed a power law decay of the measured signal with a temperature independent exponent at short-to-intermediate times for a number of liquid crystals in the isotropic phase near the isotropic-nematic transition and supercooled molecular liquids above the mode coupling theory critical temperature. In this work, the authors investigate the temperature dependence of short-to-intermediate time orientational relaxation in a model thermotropic liquid crystal across the isotropic-nematic transition and in a binary mixture across the supercooled liquid regime in molecular dynamics simulations. The measure of the experimentally observable optical Kerr effect signal is found to follow a power law decay at short-to-intermediate times for both systems in agreement with recent experiments. In addition, the temperature dependence of the power law exponent is found to be rather weak. As the model liquid crystalline system settles into the nematic phase upon cooling, the decay of the single-particle second-rank orientational time correlation function exhibits a pattern that is similar to what has been observed for supercooled liquids.     

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.     

Nanostructural organization and anion effects on the temperature dependence of the optical Kerr effect spectra of ionic liquids

The intermolecular spectra of three imidazolium ionic liquids were studied as a function of temperature by the use of optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids comprise the 1,3-pentylmethylimidazolium cation ([C(5)mim]+), and the anions, bromide (Br-), hexafluorophosphate (PF(6)-), and bis(trifluoromethanesulfonyl)imide (NTf(2)-). Whereas the optical Kerr effect (OKE) spectrum of [C(5)mim][NTf(2)] is temperature-dependent, the OKE spectra of [C(5)mim]Br and [C(5)mim][PF6] are temperature-independent. These results are surprising in light of the fact that the bulk densities of these room temperature ionic liquids (RTILs) are temperature-dependent. The temperature independence of the OKE spectra and the temperature dependence of the bulk density in [C(5)mim]Br and [C(5)mim][PF(6)] suggest that there are inhomogeneities in the densities of these liquids. The existence of density inhomogeneities is consistent with recent molecular dynamics simulations that show RTILs to be nanostructurally organized with nonpolar regions arising from clustering of the alkyl chains and ionic networks arising from charge ordering of the anions and imidazolium rings of the cations. Differences in the temperature dependences of the OKE spectra are rationalized on the basis of the degree of charge ordering in the polar regions of the RTILs.     

Molecular dynamics investigation with the time resolved optical Kerr effect on the CS2-C6H6 mixtures

An investigation of the molecular dynamics in pure liquids and in mixtures through the technique of time resolved optical Kerr effect is performed. The samples studied were the mixtures of carbon disulfide (CS(2)) with benzene (C(6)H(6)). The molecular dynamics of the pure liquids is briefly discussed while the main results are obtained for the mixtures. A slow dynamics component is observed for the optical heterodyne detected optical Kerr effect transient decaying exponentially with time constants on picosecond time scale. The fast subpicosend time relaxations are analyzed in terms of the nondiffusive component of the spectral response that is associated with the molecular dynamics. The modifications of the spectrum are quantified, and the explanation of the observed changes is given in terms of the structural interaction configurations that produced changes in the intermolecular potential within which the molecules execute librational motions.     

Dynamics in supercooled ionic organic liquids and mode coupling theory analysis

Optically heterodyne-detected optical Kerr effect experiments are applied to study the orientational dynamics of the supercooled ionic organic liquids N-propyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (PMPIm) and 1-ethyl-3-methylimidazolium tosylate (EMImTOS). The orientational dynamics are complex with relaxation involving several power law decays followed by a final exponential decay. A mode coupling theory (MCT) schematic model, the Sj?gren model, was able to reproduce the PMPIm data very successfully over a wide range of times from 1 ps to hundreds of ns for all temperatures studied. Over the temperature range from room temperature down to the critical temperature Tc of 231 K, the OHD-OKE signal of PMPIm is characterized by the intermediate power law t(-1.00+/-0.04) at short times, a von Schweidler power law t(-0.51+/-0.03) at intermediate times, and a highly temperature-dependent exponential (alpha relaxation) at long times. This form of the decay is identical to the form observed previously for a large number of organic van der Waals liquids. MCT analysis indicates that the theory can explain the experimental data very well for a range of temperatures above Tc, but as might be expected, there are some deviations from the theoretical modeling at temperatures close to Tc. For EMImTOS, the orientational dynamics were studied on the ps time scale in the deeply supercooled region near its glass transition temperature. The orientational relaxation of EMImTOS clearly displays the feature associated with the boson peak at approximately 2 ps, which is the first time domain evidence of the boson peak in ionic organic liquids. Overall, all the dynamical features observed earlier for organic van der Waals liquids using the same experimental technique are also observed for organic ionic liquids.     

Effects of molecular association on polarizability relaxation in liquid mixtures of benzene and hexafluorobenzene

In this work we have studied the relaxation dynamics of the many-body polarizability anisotropy in liquid mixtures of benzene (Bz) and hexafluorobenzene (Hf) at room temperature by femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES) experiments and molecular dynamics (MD) simulations. The computed polarizability response arising from intermolecular interactions was included using the first-order dipole-induced-dipole model with the molecular polarizability distributed over the carbon sites of each molecule. We found good qualitative agreement between experiments and simulations in the features exhibited by the nuclear response function R(t) for pure liquids and mixtures. The long-time diffusive decay of R(t) was observed to vary substantially with composition, slowing down noticeably with dilution of each of the species as compared with that in the corresponding pure liquids. MD simulation shows that the effect on R(t) is due to the formation of strong and localized intermolecular association between Bz and Hf species that hinder the rotational diffusive dynamics. The formation of these Bz-Hf complexes in the liquid mixtures also modifies the rotational diffusive dynamics of the component species in such a way that cannot be explained solely in terms of a viscosity effect. Even though the computed orientational diffusive relaxation times associated with Bz and Hf are larger by a factor of approximately 2 than those from experiments, we found similar trends in experiments and simulations for these characteristic times as a function of composition. Namely, the collective and single-molecule orientational correlation times associated with Bz are observed to grow monotonically with the dilution of Bz, while those corresponding to Hf species exhibit a maximum at the equimolar composition. We attribute the quantitative discrepancy between experiments and simulations to the use of the Williams potential, which seems to overestimate the intermolecular interactions and thus predicts not only a slower translational dynamics but also a slower rotational diffusion dynamics than in real fluids.     

Intermolecular interactions and dynamics of room temperature ionic liquids that have silyl- and siloxy-substituted imidazolium cations

The intermolecular interactions and dynamics of novel ionic liquids with alkylsilyl and alkylsiloxy substitutions on the cations are studied by measuring the intermolecular vibrational spectra and reorientational dynamics using femtosecond Kerr effect methods. The new ionic liquids include 1-dimethylphenylsilylmethyl-3-methylimidazolium (PhSi-mim+), and 1-methyl-3-pentamethyldisiloxymethylimidazolium (SiOSi-mim+) cations paired with the bis(trifluoromethylsulfonyl)imide (NTf(2)-) anion. Measured ionic liquid viscosities are surprisingly low for such bulky cation substituents. DFT electronic structure calculations on the isolated ions provide additional information about the electrostatic interactions.     

On the determination of molecular hyperpolarizabilities by combining data from the Kerr effect and from electrically induced NMR line splitting

It is shown that in the calculation of the contribution to the Kerr effect in polar liquids by the hyperpolarizabilities, the effective field should be taken equal to the sum of the Lorentz field and the reaction field. Calculation of first hyperpolarizabilities on this basis by combining values of the Kerr constant with values of the alignment from electrically induced line splitting in NMR, yields for strongly polar molecules (μ ≈ 4 D) values that are smaller by an order of magnitude than those from previous calculations on the same effects, but that compare more favourably with other data.     

Dynamics of a discotic liquid crystal in the isotropic phase

Optically heterodyne-detected optical Kerr effect (OHD-OKE) experiments are conducted to study the orientational dynamics of a discotic liquid crystal 2,3,6,7,10,11-hexakis(pentyloxy)triphenylene (HPT) in the isotropic phase near the columnar-isotropic (C-I) phase transition. The OHD-OKE signal of HPT is characterized by an intermediate power law t(-0.76+/-0.02) at short times (a few picoseconds), a von Schweidler power law t(-0.26+/-0.01) at intermediate times (hundreds of picoseconds), and an exponential decay at long times (tens of nanoseconds). The exponential decay has Arrhenius temperature dependence. The functional form of the total time dependent decay is identical to the one observed previously for a large number of molecular supercooled liquids. The mode coupling theory schematic model based on the Sjogren [Phys. Rev. A 33, 1254 (1986)] model is able to reproduce the HPT data over a wide range of times from <1 ps to tens of nanoseconds. The studies indicate that the HPT C-I phase transition is a strong first order transition, and the dynamics in the isotropic phase display a complex time dependent profile that is common to other molecular liquids that lack mesoscopic structure.     

Pīcosecond time resolution of stimulated Raman of alcohols,and their relationship to the generation of a picosecond continuum

The simultaneous time and frequency resolved spectra of stimulated Raman scattering (SRS) generated in D₂O, H₂O alcohols and diols by picosecond pulses are utilized to measure the vibrational relaxation of these liquids.The relationship between this SRS and the origin and spectral width of a broadband continuum is examined. It is shown that strong experimental evidence exists suggesting that in these liquids under a high power condition the SRS plays a major role in the existence and extent of the continuum.     

temperature-dependent orientational dynamics of 1,n-dicyano n-alkanes

Ultrafast optical Kerr effect spectroscopy has been used to study the temperature-dependent orientational dynamics of 1,n-dicyano n-alkane liquids ranging from dicyanomethane to 1,8-dicyanooctane. The dependence of the reorientational times on temperature and viscosity is consistent with the molecules adopting a largely extended structure in the liquid state, with a preference for gauche conformations at the methylenes bonded to the cyanide groups. The data are also suggestive of temperature-dependent, collective structural rearrangements in these liquids.     

Temperature-dependent optical Kerr effect spectroscopy of aromatic liquids

Ultrafast optical Kerr effect (OKE) spectroscopy has been used to study the temperature-dependent dynamics of five aromatic liquids: benzene, benzene-d(6), hexafluorobenzene, mesitylene, and 1,3,5-trifluorobenzene. The intermediate response time of all of the liquids was found to scale with the collective orientational correlation time, as has been observed for other simple liquids. The spectra of hexafluorobenzene, 1,3,5-trifluorobenzene, and mesitylene are qualitatively different from those of the other liquids and exhibit different behavior with temperature. These spectra allow us to assess the influence of different molecular parameters on the shape of the OKE spectrum. On the basis of these data, we propose a model that links the differences in the OKE spectra to corresponding differences in the local ordering of the liquids.     

Why are viscosities lower for ionic liquids with -CH2Si(CH3)3 vs -CH2C(CH3)3 substitutions on the imidazolium cations?

We have prepared novel room temperature ionic liquids (RTILs) with trimethylsilylmethyl (TMSiM)-substituted imidazolium cations and compared the properties of these liquids with those for which the TMSiM group is replaced by the analogous neopentyl group. The ionic liquids are prepared with both tetrafluoroborate (BF(4)(-)) and bis(trifluoromethylsulfonyl)imide (NTf(2)(-)) anions paired with the imidazolium cations. At 22 degrees C, the TMSiM-substituted imidazolium ILs have shear viscosities that are reduced by a factor of 1.6 and 7.4 relative to the alkylimidazolium ILs for the NTf(2)(-) and BF(4)(-) anions, respectively. To understand the effect of silicon substitution on the viscosity, the charge densities have been calculated by using density functional theory electronic structure calculations. The ultrafast intermolecular, vibrational, and orientational dynamics of these RTILs have been measured by using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). The intermolecular dynamical spectrum provides an estimate of the strength of interactions between the ions in the RTILs, and provides a qualitative explanation for the observed reduction in viscosity for the silicon-substituted RTILs.     

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < ω < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (～19 A?) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids.     

Relaxation of the optical Kerr effect of anisotropic molecules in mixed liquids

The relaxation time of the Kerr effect of nitrobenzene and m-nitrotoluene in various mixtures with carbon tetrachloride and various alcohols was determined by measuring the kinetics of the Kerr effect using picosecond laser techniques. These measurements yield information on the rotational motion of molecules in liquids. The relaxation time data are interpreted in terms of an effective local viscosity effect, pair correlation, and coupling of rotational motion with shear modes.     

Shape and electrostatic effects in optical Kerr effect spectroscopy of aromatic liquids

We present a detailed, temperature-dependent, optical Kerr effect (OKE) study of pyridine, pyridine-d(5), 2,4,6-trifluoropyridine, 2,4,6-trimethylpyridine, and 1,3,5-tris(trifluoromethyl)benzene. By combining these data with those for other aromatic liquids that we have studied previously (Loughnane, B. J.; Scodinu, A.; Fourkas J. T. J. Phys. Chem. B, 2006, 110, 5708), we are able to assess the relative importance of molecular shape and electrostatic forces in determining the form of the OKE reduced spectral density for such liquids.     

A mode coupling theory description of the short- and long-time dynamics of nematogens in the isotropic phase

Optical heterodyne-detected optical Kerr effect (OHD-OKE) experimental data are pre-sented on nematogens 4-(trans-4-n-octylcyclohexyl)isothiocyanatobenzene (8-CHBT), and 4-(4-pentyl-cyclohexyl)-benzonitrile (5-PCH) in the isotropic phase. The 8-CHBT and 5-PCH data and previously published data on 4-pentyl-4-biphenylcarbonitrile (5-CB) are analyzed using a modification of a schematic mode coupling theory (MCT) that has been successful in describing the dynamics of supercooled liquids. At long time, the OHD-OKE data (orientational relaxation) are well described with the standard Landau-de Gennes (LdG) theory. The data decay as a single exponential. The decay time diverges as the isotropic to nematic phase transition is approached from above. Previously there has been no theory that can describe the complex dynamics that occur at times short compared to the LdG exponential decay. Earlier, it has been noted that the short-time nematogen dynamics, which consist of several power laws, have a functional form identical to that observed for the short time behavior of the orientational relaxation of supercooled liquids. The temperature-dependent orientational dynamics of supercooled liquids have recently been successfully described using a schematic mode coupling theory. The schematic MCT theory that fits the supercooled liquid data does not reproduce the nematogen data within experimental error. The similarities of the nematogen data to the supercooled liquid data are the motivation for applying a modification of the successful MCT theory to nematogen dynamics in the isotropic phase. The results presented below show that the new schematic MCT theory does an excellent job of reproducing the nematogen isotropic phase OHD-OKE data on all time scales and at all temperatures.     

Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures

This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).