Dynamics of sorbitol and maltitol over a wide time-temperature range

The relaxation behaviour of two molecular glass-forming systems, namely sorbitol and maltitol, are investigated in the large temperature range relevant to the glass-transition. These data are obtained by combining three techniques, i.e. low-frequency mechanical spectroscopy, medium and high frequency dielectric spectroscopy, and viscosity measurements. This procedure allows to determine the relaxation map of these polyols on a wide time range [10^-9-10⁷ s]. Two different relaxation processes can be observed. The principal α-relaxation process exhibits a complex behaviour, comprising a non-Arrhenius temperature dependence above T _g (supercooled liquid state), and an Arrhenius behaviour below T _g (glassy state). A secondary β-relaxation is observed at higher frequencies with an Arrhenius temperature dependence. The secondary process appears in the same time-temperature range in both polyols. Consequently the molecular root of this relaxation is most likely the same in these complementary chemical systems. On the other hand, the time scale on which the α and β processes cross is very different for these two polyols. We relate this feature to the differences in the relative contributions of intra and inter-molecular interactions due to the different chemical architecture of these polyols.     

Nuclear magnetic spin-lattice relaxation and molecular motion in solid white phosphorus and in liquid phosphorus

The ³¹P spin-lattice relaxation rates have been measured in solid white phosphorus and in liquid phosphorus over the temperature range 110 K to 400 K and at Larmor frequencies of 10 MHz and 30 MHz. The contributions to the measured relaxation rate from the different interactions have been separated. In the low-temperature, crystalline phase there are important contributions to the relaxation rate from the anisotropic chemical shielding and the intramolecular dipole-dipole interactions which are modulated by the reorientational motion of the molecule. Interference effects between these two interactions, which are important in liquids, are demonstrated to be quenched by the strong dipolar interactions in the solid. The reorientational correlation time is given by

and the chemical shielding anisotropy by

In the high-temperature, plastic-crystalline phase the reorientational correlation time is

as obtained from the anisotropic chemical shielding relaxation rate which is separated from the other contributions by its quadratic dependence on the Larmor frequency. Using this τ _R the intramolecular dipole-dipole relaxation rate is calculated. The contribution from the translational diffusion modulated intermolecular dipole-dipole interaction is calculated from the self-diffusion coefficient. When these contributions are subtracted from the observed relaxation rate, there remains a frequency-independent relaxation rate, proportional to 1/δ _R , which is attributed to the spin-rotational interaction. The latter is shown to be quantitatively consistent with large-angle reorientational jumps of the P₄ molecules by 120° about their C _3v axes. The relaxation in the liquid phase is dominated by the spin-rotational interaction and the expression representing the spin-rotational relaxation rate is the same as the one derived in the plastic-crystalline phase. The mechanism of molecular reorientation in the liquid is therefore the same as in the plastic-crystalline phase.     

Detecting columnar deformations in a supermesogenic octapode by proton NMR relaxometry

We used proton ( ¹H nuclear magnetic relaxation (NMR) dispersions to study the molecular dynamics in the isotropic phase and mesophases (nematic and columnar hexagonal) of a supermesogenic octapode formed by laterally connecting calamitic mesogens to an inorganic silsesquioxane cube through flexible spacers. The dispersions of the spin-lattice relaxation time (T₁) are interpreted through relaxation mechanisms used for the study of molecular dynamics in low-molar-mass liquid crystals but adapted to the case of liquid crystalline supermolecules. At high frequencies (above 10MHz) the behaviour of the T₁ with the Larmor frequency is similar for all phases and is ascribed to local reorientations and/or rotations. At intermediate and low frequencies (below 10MHz) our results show notable differences in the T₁ behaviour with respect to the mesophases. The nematic (N) and isotropic (Iso) phases’ low-frequency results are similar and are interpreted for both phases in terms of order director fluctuations (ODF), revealing that even in the isotropic phase local nematic order is detected by proton NMR relaxometry. Local nematic order in the Iso phase is interpreted in terms of the presence of nematic cybotactic clusters induced by the interdigitation of mesogens that is promoted by the silsesquioxane octapode molecular structure. In the columnar hexagonal (Col _h phase, the T₁ dispersions show that elastic columnar deformations (ECD) dominate the nuclear magnetic relaxation below 10MHz. This result shows that the columnar packing of the octapode clearly restricts the collective fluctuations of the mesogenic units inspite of their local nematic order.     

13C relaxation studies: dipolar versus spin rotation mechanisms for camphor

The dipolar and the spin-rotation mechanism are both involved in the relaxation of the ¹³C nuclei. Their respective contributions are evaluated from the nuclear Overhauser effect in the presence and absence of Cr(acac)₃, and confirmed through the study of the temperature dependence of T ₁. The molecular rotation appears to be isotropic, and to proceed according to the Debye diffusion mechanism at 296 K.     

Dynamics of α-Tocopherol Acetate: Proton Relaxation Studies Supported by Molecular Dynamics Simulations

Dynamical properties of α-tocopherol acetate (commonly known as vitamin E) have been investigated in a broad temperature range (below and above the glass transition) by means of proton spin–lattice relaxation. Two distinct relaxation processes have been detected in the studied temperature range. One of them, present in the solid phase, has been attributed to reorientation of methyl groups. In order to identify the motional process leading to the proton relaxation above the glass transition temperature (T _g), molecular dynamics (MD) simulations have been performed, which provided time correlation functions for several internuclear vectors in the molecule. The high-temperature relaxation process is primarily due to dynamics of the aromatic rings of the tocopherol molecule; however, a considerable contribution of diffusion of the aliphatic chain cannot be excluded. Comparing the nuclear magnetic resonance (NMR) results with MD and relaxation data of dielectric spectroscopy (DS) available in the literature (K. Kamiński, S. Maślanka, J. Zioło, M. Paluch, K.J. McGrath, C.M. Roland, Phys Rev E 75:011903-7, 2007; E. Szwajczak, J. Świergiel, R. Stagraczyński, J. Jadżyn, Phys Chem Liq 47:460–466, 2009), the motional process observed in NMR relaxation studies above T _g has been identified with the δ process observed in DS.     

A Study on Photoacoustic Phase Spectra of Rare Earth Complexes with Oxine

Photoacoustic phase is the time delay that occurs from light to acoustic signal. the phase includes two components: one is the time delay that occurs during the process in which light absorbed by a sample converts into heat; the other is the time delay caused from heat to acoustic signal. a modified formula of PA phase is presented based on the R-G theory considering the phase caused by non-radiative relaxation processes. the phase is associated with absorption coefficient (β), thermal diffusion length of sample (μ_s), the longest lifetime of all excited states (r), and the ratio of rapid to slow heat component (R). When the photoacoustic signal is saturated the phase is associated with only T and R. the effect of different rare earth ions on the PA phase spectra of the ligand (oxine) in the rare earth complexes are reported and are well explained by using the phase formula of PA saturation.     

NMRON studies of the antiferromagnetic and paramagnetic phases of54Mn-MnCl2 · 4H2O

Pulsed NMRON, CW NMRON and thermal NMR-NO methods have been utilized to study⁵⁴Mn-MnCl₂ · 4H₂O. The⁵⁴Mn spin-lattice relaxation timeT ₁ in zero applied field has been measured between 35 and 90 mK in the antiferromagnetic phase. Above 65 mK the dominant relaxation mechanism is a Raman process with the electronic magnons, but at lower temperatures a direct process takes over. NMRON has been observed for the first time in the paramagnetic phase, and a line width of 300 kHz, with both homogeneous and inhomogeneous contributions, is observed. In the antiferromagnetic phase the line width is 35 kHz, and there are also homogeneous and inhomogeneous contributions. The dependence ofT ₁ for the⁵⁴Mn spins on field and temperature was studied in the paramagnetic phase. AT ₁ minimum centred atB ₀=2.64 T was observed. The hyperfine parameter <⁵⁴ AS>/h=−513.6(3) MHz in the paramagnetic phase, and comparison with the value in the antiferromagnetic phase gives 0.013(1) for the zero point spin deviation.     

Mechanism of high-temperature heat capacity of tungsten: Study of relaxation processes

It is experimentally shown that, in addition to fast relaxation, a slow relaxation process controlled by vacancy diffusion contributes to the high-temperature heat capacity C_p of tungsten. To account for the existence of contributions from two relaxation processes to C_p, it is suggested to consider the finite time required for the equilibrium density of transient complexes to set in.     

<Superscript>63,65</Superscript>Cu NMR study of low-frequency spin dynamics in the infinite-layer antiferromagnetic compound SrCuO<Subscript>2</Subscript>

The spin-lattice and spin-spin relaxation times have been measured for ^63,65Cu NMR in the infinite-layer anti-ferromagnet SrCuO₂ in the ordered state for temperatures from 4.2 to 361 K. In the region of low temperatures (T≤250 K), both relaxation processes are of the same nature and the main contribution to the relaxation rate is associated with the diffusion of a small number of holes with an activation energy of ～42 meV. In the high-temperature range (T > 250 K), contributions to the transverse relaxation rate exhibit redistribution and this relaxation process is determined predominantly by indirect interactions.     

N.M.R. study of solid perfluorocyclobutane

spin-lattice relaxation times and linewidth measurements for fluorine nuclei in solid perfluorocyclobutane are presented. The results are discussed in terms of D _2d molecular species performing fast internal motion. The relaxation measurements corroborate the existance of four solid-solid phase transitions and give some insight into their nature. The activation energies for molecular reorientation and self-diffusion processes are found to be 28·0 and 32·2 kJ mol^-1, respectively.     

Emulation of petroleum well-logging D-T2 correlations on a standard benchtop spectrometer

An experimental protocol is described that allows two-dimensional (2D) nuclear magnetic resonance (NMR) correlations of apparent diffusion coefficient D_app and effective transverse relaxation time T_2,eff to be acquired on a bench-top spectrometer using pulsed field gradients (PFG) in such a manner as to emulate D_app − T_2,eff correlations acquired using a well-logging tool with a fixed field gradient (FFG). This technique allows laboratory-scale NMR measurements of liquid-saturated cored rock to be compared directly to logging data obtained from the well by virtue of providing a comparable acquisition protocol and data format, and hence consistent data processing. This direct comparison supports the interpretation of the well-logging data, including a quantitative determination of the oil/brine saturation. The D − T₂ pulse sequence described here uses two spin echoes (2SE) with a variable echo time to encode for diffusion. The diffusion and relaxation contributions to the signal decay are then deconvolved using a 2D numerical inversion. This measurement allows shorter relaxation time components to be probed than in conventional diffusion measurements. A brief discussion of the numerical inversion algorithms available for inverting these non-rectangular data is included. The PFG-2SE sequence described is well suited to laboratory-scale studies of porous media and short T₂ samples in general.     

Separation of Anisotropy and Exchange Broadening Using N CSA–N–H Dipole–Dipole Relaxation Cross-Correlation Experiments

Based on the measurement of cross-correlation rates between ¹⁵N CSA and ¹⁵N–¹H dipole–dipole relaxation we propose a procedure for separating exchange contributions to transverse relaxation rates (R₂ = 1/T₂) from effects caused by anisotropic rotational diffusion of the protein molecule. This approach determines the influence of anisotropy and chemical exchange processes independently and therefore circumvents difficulties associated with the currently standard use of T₁/T₂ ratios to determine the rotational diffusion tensor. We find from computer simulations that, in the presence of even small amounts of internal flexibility, fitting T₁/T₂ ratios tends to underestimate the anisotropy of overall tumbling. An additional problem exists when the N–H bond vector directions are not distributed homogeneously over the surface of a unit sphere, such as in helix bundles or β-sheets. Such a case was found in segment 4 of the gelation factor (ABP 120), an F-actin cross-linking protein, in which the diffusion tensor cannot be calculated from T₁/T₂ ratios. The ¹⁵N CSA tensor of the residues for this β-sheet protein was found to vary even within secondary structure elements. The use of a common value for the whole protein molecule therefore might be an oversimplification. Using our approach it is immediately apparent that no exchange broadening exists for segment 4 although strongly reduced T₂ relaxation times for several residues could be mistaken as indications for exchange processes.     

Dielectric and orientational properties of nematogenic 4-<Emphasis Type="Italic">n</Emphasis>-octyl(4′-cyanophenyl)benzoate

Experimental studies of the dielectric properties in the nematic and isotropic phases of 4-cyanophenyl-4′-n-octylbenzoate (8CPB) have been performed in the frequency range from 50 kHz to 100 MHz. The relaxation process related to the rotation around the short molecular axis has been analysed. The results obtained have revealed that in the vicinity of the I-N phase transition, the molecular subdiffusional rotation process occurs. It is connected with the pretransitional effects which are observed both in the static and dynamic dielectric measurements. On the basis of the temperature dependence of the relaxation time in the nematic and isotropic phases, the orientational order parameter 〈P₂〉 has been determined. The values of 〈P₂〉 obtained in this way have been compared with those evaluated from the measurements of the polarized electronic absorption of the dichroic dye, dissolved as guest probe in the mesogenic host.     

Temperature dependence of elastic moduli for solid C60

The attenuation and velocity of ultrasonic waves (at a frequency of ～4 MHz) along the 〈111〉 and 〈100〉 directions in solid C₆₀ single-crystal samples are measured in the temperature range 100–300 K. The temperature dependences of the complete set of elastic constants for C₆₀ fullerite are determined from the experimental data. It is shown that the specific features in the behavior of the elastic moduli near the orientational phase transition temperature are associated with different contributions of the relaxation processes to the effective elastic moduli. The activation volume and deformation potentials for the ground and excited states of the C₆₀ low-temperature phase are evaluated from the results obtained in this work and the data available in the literature.     

Frequency and temperature amplitude dependence of complex heat capacity in the melting region of polymers

Amplitude and frequency dependence of reversible melting of polycaprolactone (PCL) and an ethylene octene copolymer (EOM) were studied using temperature-modulated differential scanning calorimetry (TMDSC) (2?10^?1 Hz <f < 0.05 Hz) and shear spectroscopy (dynamic mechanical analysis, DMA) (5?10^?4 Hz < f < 100 Hz). It was found that the excess heat capacity of PCL is constant for temperature amplitudes in the range 5 mK < A_T < 2 K. The excess heat capacity decreases with frequency of temperature perturbation and tends to zero at about 0.1 Hz and 100 Hz for PCL and EOM, respectively. The constant excess heat capacity and the frequency dependence support the idea that reversible melting is related to a relaxation process on the surface of the polymer crystals. The occurrence of such a relaxation process was shown by shear modulus measurements in the same frequency and temperature region. The relaxation process is, in the melting region, much slower than main relaxation (glass transition). At low temperatures, a crossover can be seen, indicating the independence of both processes because of spatial separation. The main relaxation is related to the melt, while the other is related to the crystal surface.     

Theoretical investigations of rotational phenomena and dielectric properties in a nematic liquid crystal

The molecular dynamics (MD) simulation, based on a realistic atom-atom interaction potential, was performed on 4-n-pentyl-4'-cyanobiphenyl (5CB) in the nematic phase. The rotational viscosity coefficients (RVCs) γ _i, (i = 1, 2) and the ratio of the RVCs λ = - γ ₂/γ ₁ were investigated. Furthermore, static and frequency-dependent dielectric constants and ε were calculated using parameters obtained from the MD simulation. Time correlation functions were computed and used to determine the rotational diffusion coefficient, D _⊥. The RVCs and λ were evaluated using the existing statistical-mechanical approach (SMA), based on a rotational diffusion model. The SMA rests on a model in which it is assumed that the reorientation of an individual molecule is a stochastic Brownian motion in a certain potential of mean torque. According to the SMA, γ _i are dependent on the orientational order and rotational diffusion coefficients. The former was characterized using: i) orientational distribution function (ODF), and ii) a set of order parameters, both derived from analyses of the MD trajectory. A reasonable agreement between the calculated and experimental values of γ _i and λ was obtained. Received 22 March 2000 and Received in final form 8 October 2000     

Lineshapes of the 172 and 602 GHz rotational transitions of HCN

Experimental lineshapes of the 172 and 602 GHz millimeter lines of HC¹⁵N in collision with H₂, N₂, O₂, CH₃CN and some rare gases are studied for the purpose of atmospheric applications and detailed collision analysis. Using of a sensitive frequency modulation technique allows highlighting clear deviations from the usual Voigt profile, these departures being generally considered as related to molecular diffusion effects or to the dependence of collisional relaxation rates on molecular speeds. Except the light buffer gases H₂ and He, the linefits using the Galatry profile lead to nonlinear pressure dependencies of relaxation rates, that rules out the frequent hypothesis of an exclusive role of molecular diffusion (Dicke effect). This observation is shown to be in accordance with the fact that optical radii related to relaxation are usually greater than kinetic Lennard-Jones radii tied to diffusion. In contrast, the actual lineshapes are well reproduced by the Speed-Dependent Voigt profile taking into account the speed dependence of relaxation rates which display linear pressure dependencies. For the particular cases of the N₂- and Ar-HCN pairs, the experimental results are rather well explained by semi-classical computations based on the Robert–Bonamy formalism improved by the model of exact trajectories. These computations show that relaxation rates are proportional to some power of the colliders’ relative speed. A detailed comparison of relaxation parameters deduced from low-pressure experiments with Galatry and Speed-Dependent Voigt profiles allows to infer that the optical diffusion rates are much smaller that kinetic ones, so that the experimental lineshapes depend nearly exclusively on the speed dependence of relaxation rates and are weakly affected by molecular diffusion effects. Extension of these conclusions to other molecules of atmospheric interest is discussed. Finally, an appendix presents unpublished results dealing with the collisional relaxation of some rotational lines of HC¹⁵N (at 258 GHz for different temperatures and at 344 GHz) and HC¹⁴N (at 355 GHz).     

Dielectric spectroscopy of the SmQ* phase

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmC_A* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmC_A* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmC_A*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmC_A* phase. Its relaxation frequency is similar to P_H relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*–Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.