Rotational motion in liquid water is anisotropic: a nuclear magnetic resonance and molecular dynamics simulation study

Experimental NMR measurements of the deuterium and (17)O T(1) relaxation times in deuterium-enriched liquid water have been performed from 275 to 350 K. These relaxation times can yield rotational correlation times of appropriate molecule-fixed unit vectors if the quadrupole coupling constants and asymmetry parameters are known. We determine the latter from ab initio studies of water clusters and experimental chemical shift measurements. We find that the rotational correlation time for the OD bond vector in D(2)(16)O varies from 5.8 ps at 275 K to 0.86 ps at 350 K, and that the rotational correlation time for the out-of-plane vector of dilute D(2)(17)O in D(2)(16)O varies from 4.4 ps at 275 K to 0.64 ps at 350 K. These results indicate that the rotational motion of water is anisotropic. Molecular dynamics simulations of liquid water are in good agreement with these experiments at the higher temperatures, but the simulation results are considerably faster than experiment at the lower temperatures.     

1H NMR study of internal motions and quantum rotational tunneling in (CH3)4NGeCl3

(CH3)4NGeCl3 is prepared, characterized and studied using 1H NMR spin lattice relaxation time and second moment to understand the internal motions and quantum rotational tunneling. Proton second moment is measured at 7 MHz as function of temperature in the range 300-77 K and spin lattice relaxation time (T1) is measured at two Larmor frequencies, as a function of temperature in the range 270-17 K employing a homemade wide-line/pulsed NMR spectrometers. T1 data are analyzed in two temperature regions using relevant theoretical models. The relaxation in the higher temperatures (270-115 K) is attributed to the hindered reorientations of symmetric groups (CH3 and (CH3)4N). Broad asymmetric T1 minima observed below 115 K down to 17 K are attributed to quantum rotational tunneling of the inequivalent methyl groups.     

Phosphinic derivative of DTPA conjugated to a G5 PAMAM dendrimer: an 17O and 1H relaxation study of its Gd(III) complex

A DTPA-based chelate containing one phosphinate group was conjugated to a generation 5 polyamidoamine (PAMAM) dendrimer via a benzylthiourea linkage. The Gd(III) complex of this novel conjugate has potential as a contrast agent for magnetic resonance imaging (MRI). The chelates bind Gd3+via three nitrogen atoms, four carboxylates and one phosphinate oxygen, and one water molecule completes the inner coordination sphere. The monomer Gd(III) chelates bearing nitrobenzyl and aminobenzyl groups ([Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-) as well as the dendrimeric Gd(III) complex G5-(Gd(DTTAP))63) were studied by multiple-field, variable temperature 17O and 1H NMR. The rate of water exchange is faster than that of [Gd(DTPA)(H2O)]2- and very similar on the two monomeric complexes (8.9 and 8.3 x 10(6) s-1 for [Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-, respectively), while it is decreased on the dendrimeric conjugate (5.0 x 10(6) s-1). The Gd(III) complex of the dendrimer conjugate has a relaxivity of 26.8 mM-1 s-1 at 37 degrees C and 0.47 T (corresponding to 1H Larmor frequency of 20 MHz). Given the contribution of the second sphere water molecules to the overall relaxivity, this value is slightly higher than those reported for similar size dendrimers. The experimental 17O and 1H NMR data were fitted to the Solomon-Bloembergen-Morgan equations extended with a contribution from second coordination sphere water molecules. The rotational dynamics of the dendrimeric conjugate was described in terms of global and local motions with the Lipari-Szabo approach.     

Measuring molecular dynamics and activation energies for quaternary acyclic ammonium and cyclic pyrrolidinium ionic liquids using 14N NMR spectroscopy

The (14)N NMR spin-lattice (R(1)) and spin-spin (R(2)) relaxation rates were determined as a function of temperature for a series of tetra-alkyl acyclic ammonium and cyclic pyrrolidinium ionic liquids (ILs). Through the use of the R(2)/R(1) ratio method, it was shown that for the majority of these ILs, the reorientational dynamics are not in the extreme narrowing regime, but instead are in the dispersive relaxation regime, thus allowing a unique solution for the correlation time to be determined. The temperature variation of the R(2) relaxation rate, along with the temperature variation of the calculated correlation times, allowed activation energies for the reorientational dynamics to be measured and compared. In addition, these NMR relaxation experiments enabled the (14)N quadrupolar coupling product to be extracted, which revealed surprising temperature dependence. Collectively, the (14)N NMR results allow the impact of cation and anion identity on the local reorientational dynamics of these ILs to be delineated.     

Communication: exploring the reorientation of benzene in an ionic liquid via molecular dynamics: effect of temperature and solvent effective charge on the slow dynamics

The rotational time correlation function (RTCF) of solute benzene molecules in the ionic liquid (1-butyl-3-methylimidazolium chloride) has been studied using classical molecular dynamics simulation. The effect of solvent charge on the functional form of RTCF was investigated by comparing four force fields for the solvent where the total charge on the anion and the cation was set to ±1e, ±0.7e, ±0.5e, and 0, respectively. For all three charged solvent models, the RTCF exhibits a long-time tail where the relaxation rate exhibits a significant slowdown. This feature is strengthened by higher solvent charges as well as lower temperatures, indicating the influence of the strong Coulombic fields arising from the solvent charges. The long-time tail is caused by the extraordinarily slow solvent structural relaxation of ionic liquids compared to the time scale of their local vibrational and librational dynamics.     

Water dynamics in ionomer membranes by field-cycling NMR relaxometry

The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimide, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows the proton motion on a time scale of microseconds to be probed. The NMR longitudinal relaxation rate R(1) measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well-suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R(1)(omega) following closely a 1/square root omega law in a low-frequency range (correlation times from 0.1 to 10 micros). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). Variations of the relaxation rates with water uptake reveal a two-step hydration process: solvation and formation of disconnected aqueous clusters near polar groups, followed by the formation of a continuous hydrogen bond network. On the contrary, in the Nafion we observed weak variations of R(1)(omega) at low frequencies. This is typical of a nonwetting behavior. At early hydration stages, R(1)(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to three-dimensional diffusion is observed.     

Nuclear magnetic resonance study of the dynamics of imidazolium ionic liquids with -CH2Si(CH3)3 vs -CH2C(CH3)3 substituents

Trimethylsilylmethyl (TMSiM)-substituted imidazolium bis(trifluoromethylsulfonyl)imide (NTf(2)-), and tetrafluoroborate (BF(4)-) ionic liquids (ILs) have lower room-temperature viscosities by factors of 1.6 and 7.4, respectively, than isostructural neopentylimidazolium ILs. In an attempt to account for the effects of silicon substitution in imidazolium RTILs and to investigate the ion dynamics, we report nuclear magnetic resonance (NMR) measurements of 1H (I = 1/2) and 19F (I = 1/2) spin-lattice relaxation times (T1) and self-diffusion coefficients (D) as a function of temperature for ILs containing the TMSiM group and, for comparison, the analogous neopentyl group. The 1H and 19F nuclei probe the dynamics of the cations and anions, respectively. The low-temperature line shapes were determined to be Gaussian, and the onset of the rigid lattice line width is correlated with the measured glass transition temperature. The spin-lattice relaxation data feature a broad T1 minimum as a function of inverse temperature for both nuclear species. The Arrhenius plots of the diffusion data for both nuclear species are found to exhibit Vogel-Tammann-Fulcher curvature. Analysis of the eta and D data generally show fractional Stokes-Einstein behavior D proportional to (T/eta)m. This is most prominent in the neopentylimidazolium BF(4)- IL with m approximately 0.66.     

On the mechanism of reorientational and structural relaxation in supercooled liquids: the role of border dynamics and cooperativity

Molecular dynamics simulation and analysis based upon the many-body potential energy landscape (PEL) are employed to characterize single molecule reorientation and structural relaxation, and their interrelation, in deeply supercooled liquid CS(2). The rotational mechanism changes from small-step Debye diffusion to sudden large angle reorientation (SLAR) as the temperature falls below the mode-coupling temperature T(c). The onset of SLAR is explained in terms of the PEL; it is an essential feature of low-T rotational dynamics, along with the related phenomena of dynamic heterogeneity and the bifurcation of slow and fast relaxation processes. A long trajectory in which the system is initially trapped in a low energy local minimum, and eventually escapes, is followed in detail, both on the PEL and in real space. During the trapped period, "return" dynamics occurs, always leading back to the trap. Structural relaxation is identified with irreversible escape to a new trap. These processes lead to weak and strong SLAR, respectively; strong SLAR is a clear signal of structural relaxation. Return dynamics involves small groups of two to four molecules, while a string-like structure composed of all the active groups participates in the escape. It is proposed that, rather than simple, nearly instantaneous, one-dimensional barrier crossings, relaxation involves activation of the system to the complex, multidimensional region on the borders of the basins of attraction of the minima for an extended period.     

Characteristic behavior of short-term dynamics in reorientation for Gay-Berne particles near the nematic-isotropic phase transition temperature

A specific transition behavior was found in the tumbling motion near the nematic-isotropic phase boundary using molecular dynamics simulations of the Gay-Berne mesogenic model under isobaric conditions at a reduced pressure P* of 2.0. The relaxation time for the motion obtained from the second-rank orientational time correlation function and the rotational diffusion coefficient showed a clear jump at the nematic-isotropic phase transition temperature. Regardless of the temperature dependence of the relaxation time, the change in the rotational diffusion coefficient evaluated from the orientational order parameters and the relaxation time agreed qualitatively with that of real mesogens. The rotational viscosity coefficients gamma(1) and gamma(2) were obtained from the simulation data for the relaxation time for the short-term dynamics and for the rotational diffusion coefficients. gamma(1) was proportional to (2), where is the second-rank orientational parameter. Furthermore, the rotational behavior of the model was compared with that of the Debye approximation in the isotropic phase.     

Variable-temperature (17)o NMR studies allow quantitative evaluation of molecular dynamics in organic solids

We report a comprehensive variable-temperature solid-state (17)O NMR study of three (17)O-labeled crystalline sulfonic acids: 2-aminoethane-1-sulfonic acid (taurine, T), 3-aminopropane-1-sulfonic acid (homotaurine, HT), and 4-aminobutane-1-sulfonic acid (ABSA). In the solid state, all three compounds exist as zwitterionic structures, NH(3)(+)-R-SO(3)(-), in which the SO(3)(-) group is involved in various degrees of O···H-N hydrogen bonding. High-quality (17)O NMR spectra have been obtained for all three compounds under both static and magic angle spinning (MAS) conditions at 21.1 T, allowing the complete set of (17)O NMR tensor parameters to be measured. Assignment of the observed (17)O NMR parameters to the correct oxygen sites in the crystal lattice was achieved with the aid of DFT calculations. By modeling the temperature dependence of (17)O NMR powder line shapes, we have not only confirmed that the SO(3)(-) groups in these compounds undergo a 3-fold rotational jump mechanism but also extracted the corresponding jump rates (10(2)-10(5) s(-1)) and the associated activation energies (E(a)) for this process (E(a) = 48 ± 7, 42 ± 3, and 45 ± 1 kJ mol(-1) for T, HT, and ABSA, respectively). This is the first time that SO(3)(-) rotational dynamics have been directly probed by solid-state (17)O NMR. Using the experimental activation energies for SO(3)(-) rotation, we were able to evaluate quantitatively the total hydrogen bond energy that each SO(3)(-) group is involved in within the crystal lattice. The activation energies also correlate with calculated rotational energy barriers. This work provides a clear illustration of the utility of solid-state (17)O NMR in quantifying dynamic processes occurring in organic solids. Similar studies applied to selectively (17)O-labeled biomolecules would appear to be very feasible.     

Determination of the (17)O Quadrupolar Coupling Constant and of the (13)C Chemical Shielding Tensor Anisotropy of the CO Groups of Pentane-2,4-dione and beta-Diketonate Complexes in Solution. NMR Relaxation Study

13C NMR relaxation times T(1) of the carbonyl groups of pentane-2,4-dione and beta-diketonate complexes Al(acac)(3) and Zr(acac)(4) (acac: pentanedionate anion) were measured for various magnetic field strengths, allowing a determination of the contribution of the chemical shift anisotropy mechanism to the total relaxation. NOE and T(1) measurements for the (13)C nucleus of the central methine carbon furnished the correlation time tau(c) for the reorientation of theses species. The chemical shift tensor anisotropy Deltasigma could be deduced and compared to the values obtained in the solid state. The quadrupolar coupling constant (QCC) of the (17)O nucleus could also be determined by measuring the line width of the (17)O NMR signal and using the tau(c) value. QCC values for the complexes are in the same range as for the pentane-2,4-dione molecule, indicating similar electronic distribution and symmetry around the oxygen atom of these different species. Deltasigma for the complexes are close together, and the values obtained in solution are approximately those obtained in the solid state. They are close to the value reported in the literature for tetraacetylethane, which can be considered as a dimer of a beta-diketone, but slight differences are observed for the individual components of the chemical shielding tensor.     

Molecular dynamics investigation of dynamical properties of phosphatidylethanolamine lipid bilayers

We describe the dynamic behavior of a 1-stearoyl-2-oleoyl-phosphatidylethanolamine (SOPE) bilayer from a 20 ns molecular dynamics simulation. The dynamics of individual molecules are characterized in terms of (2)H spin-lattice relaxation rates, nuclear overhauser enhancement spectroscopy (NOESY) cross-relaxation rates, and lateral diffusion coefficients. Additionally, we describe the dynamics of hydrogen bonding through an analysis of hydrogen bond lifetimes and the time evolution of clusters of hydrogen bonded lipids. The simulated trajectory is shown to be consistent with experimental measures of internal, intermolecular, and diffusive motion. Consistent with our analysis of SOPE structure in the companion paper, we see hydrogen bonding dominating the dynamics of the interface region. Comparison of (2)H T(1) relaxation rates for chain methylene segments in phosphatidylcholine and phosphatidylethanolamine bilayers indicates that slower motion resulting from hydrogen bonding extends at least three carbons into the hydrophobic core. NOESY cross-relaxation rates compare well with experimental values, indicating the observed hydrogen bonding dynamics are realistic. Calculated lateral diffusion rates (4 +/ -1 x 10(-8) cm(2)s) are comparable, though somewhat lower than, those determined by pulsed field gradient NMR methods.     

A benzene-core trinuclear GdIII complex: towards the optimization of relaxivity for MRI contrast agent applications at high magnetic field

A novel ligand, H(12)L, based on a trimethylbenzene core bearing three methylenediethylenetriamine-N,N,N',N'-tetraacetate moieties (-CH(2)DTTA(4-)) for Gd(3+) chelation has been synthesized, and its trinuclear Gd(3+) complex [Gd(3)L(H(2)O)(6)](3-) investigated with respect to MRI contrast agent applications. A multiple-field, variable-temperature (17)O NMR and proton relaxivity study on [Gd(3)L(H(2)O)(6)](3-) yielded the parameters characterizing water exchange and rotational dynamics. On the basis of the (17)O chemical shifts, bishydration of Gd(3+) could be evidenced. The water exchange rate, k(ex)(298)=9.0+/-3.0 s(-1) is around twice as high as k(ex)(298) of the commercial [Gd(DTPA)(H(2)O)](2-) and comparable to those on analogous Gd(3+)-DTTA chelates. Despite the relatively small size of the complex, the rotational dynamics had to be described with the Lipari-Szabo approach, by separating global and local motions. The difference between the local and global rotational correlation times, tau(lO)(298)=170+/-10 ps and tau(gO)(298)=540+/-100 ps respectively, shows that [Gd(3)L(H(2)O)(6)](3-) is not fully rigid; its flexibility originates from the CH(2) linker between the benzene core and the poly(amino carboxylate) moiety. As a consequence of the two inner-sphere water molecules per Gd(3+), their close to optimal exchange rate and the appropriate size and limited flexibility of the molecule, [Gd(3)L(H(2)O)(6)](3-) has remarkable proton relaxivities when compared with commercial contrast agents, particularly at high magnetic fields (r(1)=21.6, 17.0 and 10.7 mM(-1)s(-1) at 60, 200 and 400 MHz respectively, at 25 degrees C; r(1) is the paramagnetic enhancement of the longitudinal water proton relaxation rate, referred to 1 mM concentration of Gd(3+)).     

On the role of collective and local molecular fluctuations in the relaxation of proton intrapair dipolar order in nematic 5CB

We investigate the role that local motions and slow cooperative fluctuations have on the relaxation of the intrapair dipolar order in the nematic 5CB. With this purpose we present a theoretical and experimental systematic study which allow us to quantify the contribution from each type of molecular fluctuation to the intrapair dipolar order relaxation time, T(1D). The experimental work includes measurements of Zeeman and intrapair dipolar order relaxation times (T(1Z) and T(1D)) as a function of temperature at conventional NMR frequencies, in three complementary samples: normal and chain deuterated 4-n-pentyl-4(')-cyanobiphenyl (5CB and 5CB(d11)) and a mixture of normal 5CB and fully deuterated 4-n-pentyl-4'-cyanobiphenyl (5CB(d19)), 50% in weight. Additionally we perform T(1Z) field-cycling Larmor frequency-dependent measurements to obtain the spectral density of the cooperative fluctuations. The obtained results are as follows. (a) The cooperative molecular fluctuations have a strong relative weight in the relaxation of the intrapair dipolar order state, even at Larmor frequencies in the range of conventional NMR. (b) Alkyl chain rotations are an important relaxation mechanism of the intrapair dipolar order at megahertz frequencies. (c) Intermolecular fluctuations mediated by translational self-diffusion of the molecules is not an efficient mechanism of relaxation of the intrapair dipolar order.     

Studies on the translational and rotational motions of ionic liquids composed of N-methyl-N-propyl-pyrrolidinium (P13) cation and bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide anions and their binary systems including lithium salts

Room-temperature ionic liquids (RTIL, IL) are stable liquids composed of anions and cations. N-methyl-N-propyl-pyrrolidinium (P(13), Py(13), PYR(13), or mppy) is an important cation and produces stable ILs with various anions. In this study two amide-type anions, bis(trifluoromethanesulfonyl)amide [N(SO(2)CF(3))(2), TFSA, TFSI, NTf(2), or Tf(2)N] and bis(fluorosulfonyl)amide [N(SO(2)F)(2), FSA, or FSI], were investigated. In addition to P(13)-TFSA and P(13)-FSA, lithium salt doped samples were prepared (P(13)-TFSA-Li and P(13)-FSA-Li). The individual ion diffusion coefficients (D) and spin-lattice relaxation times (T(1)) were measured by (1)H, (19)F, and (7)Li NMR. At the same time, the ionic conductivity (σ), viscosity (η), and density (ρ) were measured over a wide temperature range. The van der Waals volumes of P(13), TFSA, FSA, Li(TFSA)(2), and Li(FSA)(3) were estimated by molecular orbital calculations. The experimental values obtained in this study were analyzed by the classical Stokes-Einstein, Nernst-Einstein (NE), and Stokes-Einstein-Debye equations and Walden plots were also made for the neat and binary ILs to clarify physical and mobile properties of individual ions. From the temperature-dependent velocity correlation coefficients for neat P(13)-TFSA and P(13)-FSA, the NE parameter 1-ξ was evaluated. The ionicity (electrochemical molar conductivity divided by the NE conductivity from NMR) and the 1-ξ had exactly the same values. The rotational and translational motions of P(13) and jump of a lithium ion are also discussed.     

Deuterium spin probes of side-chain dynamics in proteins. 2. Spectral density mapping and identification of nanosecond time-scale side-chain motions

In the previous paper in this issue we have demonstrated that it is possible to measure the five different relaxation rates of a deuteron in (13)CH(2)D methyl groups of (13)C-labeled, fractionally deuterated proteins. The extensive set of data acquired in these experiments provides an opportunity to investigate side-chain dynamics in proteins at a level of detail that heretofore was not possible. The data, acquired on the B1 domain of peptostreptococcal protein L, include 16 (9) relaxation measurements at 4 (2) different magnetic field strengths, 25 degrees C (5 degrees C). These data are shown to be self-consistent and are analyzed using a spectral density mapping procedure which allows extraction of values of the spectral density function at a number of frequencies with no assumptions about the underlying dynamics. Dynamics data from 31 of 35 methyls in the protein for which data could be obtained were well-fitted using the two-parameter Lipari-Szabo model (Lipari, G.; Szabo, A. J. Am. Chem. Soc. 1982, 104, 4546). The data from the remaining 4 methyls can be fitted using a three-parameter version of the Lipari-Szabo model that takes into account, in a simple manner, additional nanosecond time-scale local dynamics. This interpretation is supported by analysis of a molecular dynamics trajectory where spectral density profiles calculated for side-chain methyl sites reflect the influence of slower (nanosecond) time-scale motions involving jumps between rotameric wells. A discussion of the minimum number of relaxation measurements that are necessary to extract the full complement of dynamics information is presented along with an interpretation of the extracted dynamics parameters.     

Proton NMR relaxation study of molecular dynamics of chromonic liquid crystal Edicol Sunset Yellow

Proton nuclear magnetic resonance (¹H NMR) relaxometry, over about five decades in Larmor frequency, and pulsed field gradient NMR were used to study the molecular dynamics in the chromonic nematic and isotropic phases of stacked molecules of the binary mixture composed by Edicol Sunset Yellow (ESY) and deuterated water. Our results evidence that in both phases collective motions are responsible for the spin-lattice relaxation dispersion in the Larmor frequency range below 1 MHz. In the nematic phase, the collective motion are attributed to columnar undulations within the stacked molecules, while, in the isotropic phase, the results are explained by local order fluctuations due to the formation of the stacks. The high frequency dispersion was explained by individual molecular motions like rotations around and perpendicular to the stack axis, and also self-diffusion.     

Angular and frequency dependent spin relaxation study of liquid crystalline cyanobiphenyls

NMR field-cycling measurements of the Larmor frequency (v) and angular (Δ) dependences of the longitudinal proton spin relaxation time T₁ for the nematic liquid crystals 5CB and 8CB allow a more detailed analysis of the underlying molecular motions than data available previously. All T₁ (v, Δ) dispersion profiles essentially distinguish three frequency ranges where T₁ is governed by either local field effects, collective motions (director order fluctuations), or rotational and translational diffusion of individual molecules or molecular groups, respectively. The angular dependence supports and extends previous conclusions about the significance of the order fluctuation term at low (kHz) and high (MHz) Larmor frequencies; in addition it is the basis for the disentanglement of local field effects, which involve Jeener's dipolar relaxation, and of the sophisticated rotational relaxation models suggested in the literature by Dong, Nordio and Vold. It is found that Vold's third rate concept gives the best explanation of the measurements. The results on the rotational diffusion processes essentially agree with deuteron studies from the literature, but also reveal clear distinctions with regard to the anisotropy parameter σ, essentially due to the improved separation from the order fluctuation contribution.     

Positron annihilation and relaxation dynamics from dielectric spectroscopy and nuclear magnetic resonance: cis-trans-1,4-poly(butadiene)

We report a joint analysis of positron annihilation lifetime spectroscopy (PALS), dielectric spectroscopy (BDS), and nuclear magnetic resonance (NMR) on cis-trans-1,4-poly(butadiene) (c-t-1,4-PBD). Phenomenological analysis of the orthopositronium lifetime τ(3)-T dependence by linear fitting reveals four characteristic PALS temperatures: T(b1)(G)=0.63T(g)(PALS), T(g)(PALS), T(b1)(L)=1.22T(g)(PALS), and T(b2)(L)=1.52T(g)(PALS). Slight bend effects in the glassy and supercooled liquid states are related to the fast or slow secondary β process, from neutron scattering, respectively, the latter being connected with the trans-isomers. In addition, the first bend effect in the supercooled liquid coincides with a deviation of the slow effective secondary β(eff) relaxation related to the cis-isomers from low-T Arrhenius behavior to non-Arrhenius one and correlates with the onset of the primary α process from BDS. The second plateau effect in the liquid state occurs when τ(3) becomes commensurable with the structural relaxation time τ(α)(T(b2)). It is also approximately related to its crossover from non-Arrhenius to Arrhenius regime in the combined BDS and NMR data. Finally, the combined BDS and NMR structural relaxation data, when analyzed in terms of the two-order parameter (TOP) model, suggest the influence of solidlike domains on both the annihilation behavior and the local and segmental chain mobility in the supercooled liquid. All these findings indicate the influence of the dynamic heterogeneity in both the primary and secondary relaxations due to the cis-trans isomerism in c-t-1,4-PBD and their impact into the PALS response.     

A molecular dynamics computer simulation study of room-temperature ionic liquids. II. Equilibrium and nonequilibrium solvation dynamics

The molecular dynamics (MD) simulation study of solvation structure and free energetics in 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium hexafluorophosphate using a probe solute in the preceding article [Y. Shim, M. Y. Choi and H. J. Kim, J. Chem. Phys. 122, 044510 (2005)] is extended to investigate dynamic properties of these liquids. Solvent fluctuation dynamics near equilibrium are studied via MD and associated time-dependent friction is analyzed via the generalized Langevin equation. Nonequilibrium solvent relaxation following an instantaneous change in the solute charge distribution and accompanying solvent structure reorganization are also investigated. Both equilibrium and nonequilibrium solvation dynamics are characterized by at least two vastly different time scales--a subpicosecond inertial regime followed by a slow diffusive regime. Solvent regions contributing to the subpicosecond nonequilibrium relaxation are found to vary significantly with initial solvation configurations, especially near the solute. If the solvent density near the solute is sufficiently high at the outset of the relaxation, subpicosecond dynamics are mainly governed by the motions of a few ions close to the solute. By contrast, in the case of a low local density, solvent ions located not only close to but also relatively far from the solute participate in the subpicosecond relaxation. Despite this difference, linear response holds reasonably well in both ionic liquids.