Inter and Intramolecular Contributions to the Proton Dipolar and Rotating Frame Spin-Lattice Relaxation Times in the Nematic Phase of the Liquid Crystal 5CB-d 11

An isotopic dilution study of the proton dipolar and rotating frame spin-lattice relaxation times (T ₁ D and T ₁ p) in the nematic liquid crystal 4-cyano-4′-n-pentyl-d ₁₁-biphenyl (5CB-d ₁₁) at 13.8 MHz over the nematic phase temperature range was used to separate the intermolecular and intramolecular contributions to the ring proton relaxation rates. This is the first such study to be reported. Combined with our earlier proton study of inter/intra Zeeman spin-lattice relaxation (T ₁) in 5CB-d ₁₁, these data permit a critical study of the soft-mode dynamics in the system. A qualitative explanation of the T ₁ D> results is presented, but a complete explanation of the T ₁ p results is not possible with existing theory.     

Proton Spin-Lattice Relaxation Dispersion Study of the Ferroelectric Smectic Phases in Dobambc

The frequency dispersion of the proton spin-lattice relaxation rates T^?1 ₁ in the ferroelectric smectic phases of DOBAMBC has been determined in the MHz region and analyzed in terms of the order fluctuations, self-diffusion, and rotational contributions to T^?1 ₁. In the smectic C* phase the main rate determining contribution are order fluctuations with a T^?1 ₁ ∝ ν^?1/2 _L frequency dependence, whereas in the smectic H* phase the translational diffusion, which is slower than in the smectic H* phase, determines the dispersion of T^?1 ₁.     

Solid state H NMR study of molecular dynamics and domain sizes in PBT with the fullerene derivates: Decylamine-C60 and tetracyanoethylene oxide-C60

The solid-state ¹H NMR on-resonance and off-resonance techniques have been performed to study molecular dynamics and domain sizes in heterogenous nanocomposites based on poly(butylene terephthalate) and nanoparticles C₆₀ modified by n-decylamine (DA) or tetracyanoethylene oxide (TCNEO), respectively. The spin-lattice off-resonance relaxation times in the rotating frame T_1ρ^off as well as the second moment M₂ of the absorption line were analysed as a function of temperature. To determine the size of heterogeneities and characterize the morphology of the nanocomposites, the ¹H NMR spin-diffusion experiment designed by Goldman-Shen [1,2] was performed. The results from the measurements allow us to investigate the spin-diffusion phenomenon and relaxation behavior of the new nanocomposites.     

On the Phase Transition Behaviour of Binary Systems: Various Non-Nematic Solutes in Nematic Solvent (EBBA)

Phase transition behaviour of the systems of EBBA with methyl alcohol (MeOH), 1.2-dibromo-ethylene (DBE), o-xylene, m-xylene, and p-xylene has been studied. The phase diagrams for each system have been determined by the polarizing microscope. The slopes, β_n and B_i, of the nematic and the isotropic phase boundary lines in each system have been qualitatively described by the molecular field treatment proposed by Humphries. The order parameters for both cis-and trans-DBE in EBBA have been obtained from analyses of ¹H-NMR spectra. In the nematic phase, they decrease with increase in temperature. In the nematic/isotropic coexisting phase (N/I phase), the order parameter for CIS-DBE is almost independent of temperature. The proton spin-lattice relaxation times (T₁) in the MeOH/EBBA system have been measured by a pulse NM R technique. Little temperature dependence of T¹ has been found in the N/1 phase region.c     

Nuclear Spin-Lattice Relaxation in the Linear Chain Metal,NbSe3

Abstract

The nuclear spin-lattice relaxation time T ₁ of ⁹³Nb in NbSe₃ has been observed as a function of frequency v _N in the range 6-40 MHz at 4.2 K and of temperature T in the range 1.3-77 K at 10 MHz. [T ₁ T]^?1 is found to be proportional to 1/√ν corresponding to characteristic divergence of spin correlation function in 1-D system. Below ~10 MHz, a break down of the divergence is observed. The important features of the T dependence observed are a sharp minimum at ~45 K and an asymptotical approach to the metallic relation, T ₁ T= const, with decreasing T down to helium temperature. This [T ₁ T]^?1 minimum is explained by the destruction of the Fermi surface due to the CDW gap formation. The re-increase of [T ₁ T]^?1 below the CDW transition may suggest a partial recovery of the destructed Fermi surface.     

The design of spin-lattice relaxation experiments

The method of determining spin-lattice relaxation time (T ₁) of liquids by NMR is considered from two aspects: the nature of the pulse sequence and the choice of the experimental independent variable. It is shown that prediction analysis may be used to select the range, distribution, and number of measurements which minimize the amount of time required for the determination ofT ₁ to a given precision.A preliminary report of this work was presented at the 3rd National NMR Conference, Brisbane, Queensland, May 1981.     

NMR investigation of rapid structural changes and non-metal-to-metal transition in the molten eutectic Ge–Te alloy

Resonance shift, K¹²⁵, spin-lattice relaxation time, T₁ and spin–spin relaxation time, T₂ for ¹²⁵Te nuclei in molten Ge₁₅Te₈₅ and Te in deeply under-cooled state have been measured as a function of temperature. The temperature dependence of K¹²⁵ is compared with that of the extent of structural change, C, and it is shown that the rapid increase of K¹²⁵ with increasing temperature can be attributed to an increase of the density of states at the Fermi level proportional to the extent of structural change. At high temperatures, the dependences on the temperature of K¹²⁵ and T₁ conform to the Korringa relation with an enhancement factor or the relaxation mechanism expected metallic nature. At low temperatures, in contrast, the Redfield theory assuming localized spins of which the density is proportional to C can explain the overall temperature dependences of T₁ and T₂. These results provide the first clear evidence for a crossover transition from extended to localized states in the electron system accompanying the rapid structural changes.     

Low-temperature nuclear spin-lattice relaxation in glasses - homogeneous and inhomogeneous averaging

A phenomenological model is presented which is able to explain both temperature and magnetic field dependences of nuclear spin-lattice relaxation rates T₁^?1 observed recently in glasses at low temperatures. The model assumes randomly distributed defect centres, typical of glasses, producing internal fluctuating fields. The only restrictive assumption is a power law for the distance dependence of the responsible interaction. In accordance with experiment, homogeneous and inhomogeneous relaxation, corresponding to exponential and non-exponential relaxation behaviour, is predicted in the cases of rapid and slow spin diffusion, respectively. Describing the fluctuating interactions by a BPP-type spectral density and assuming an Arrhenius law for the correlation time, explicit expressions for T_-1^? are obtained. It is shown that by comparison of homogeneous and inhomogeneous relaxation data information on the type of interaction and the density of defect centres can be obtained.     

An Investigation of Molecular Reorientation in Crystalline Pyrazine by Pulse NMR and The Atom-Atom Approximation for Intermolecular Forces

Proton NMR relaxation times (T ₁, at 9.2 MHz and 18.5 MHz, and T ₁ at 18.5 MHz) have been measured for crystalline pyrazine over the temperature range 293 K to the melting point at 327 K. No evidence of a discontinuity in these data is evident at either 29°C or 35°C, where previous workers have found evidence of a phase transition using infrared, Raman, ¹⁴N NQR, calorimetric and other techniques. This result was valid for both unpurified samples and for samples obtained as the result of fractional sublimation. With the assistance of potential energy calculations using the atom-atom approximation for intermolecular forces, the nature of the motional process responsible for the spin-lattice relaxation has been proposed to be an in-plane flip by 180 degrees; this proposal appears to be consistent with all experimental information available for the low-temperature phase stable below 29°C. In addition, the nature of the first phase transition at 29°C has been similarly investigated; it is suggested that this involves an inplane rotation by 90 degrees of just one of the two molecules in the unit cell. Again, this suggestion seems capable of rationalising all available information concerning this transition, although it is possibly not unique in this regard.     

Effect of Pressure on Antiferromagnetic Transition in Alkali-Electro-Sodalite

Abstract

Pressure (0–19 kbar) and temperature (4–300 K) dependent EPR study of Sodium-Electro-Sodalite (SES) is presented. SES, which consists of a bcc sub-lattice of F-centers supported by a zeolite-like framework, is known to be a Mott insulator at room temperature. On cooling, SES undergoes an AF transition at 48±2 K providing the first example of an s-electron antiferromagnet. We find that the width of the EPR resonance above T _N is influenced not only by a strong exchange interaction, but also by a fast spin-lattice relaxation. Also, with increasing pressure, T _N decreases linearly and extrapolates to 0 K at about 65 kbar. The reason for this seemingly unexpected behavior is briefly discussed.     

NMR Studies of (TMTSF)2PF6

Abstract

Pulsed NMR determinations of the relaxation times T₂, T₂* and T₁, as a function of temperature and field, for the methyl group protons in (TMTSF)₂PF₆ are reported. Below the metal-insulator transition (T_MI)T₂* shortens while T₂ increases, indicating a line which is inhomogeneously broadened due to the onset of a SDW. The SDW also contributes to the spin-lattice relaxation rate, T₁ ^?1, in the neighborhood of T_MI. A frequency dependent maximum in T₁ ^?1 is observed near 20K and is attributed to methyl group rotation. A frequency independent maximum at 58K suggests a structural phase transition involving rearrangement of the methyl and PF₆ groups.     

Relaxation effects in glassy selenium

Thermal relaxation phenomena were measured in samples of both melt-quenched and evaporated selenium. On the basis of earlier studies, the two methods of preparation produced samples with polymeric chain concentrations of 30–50% and 0% respectively; the rest of the material was in the form of eight member rings. The relaxation peak occurred between 320 and 330 K, and had an activation energy of ≈22.5 kcal/mole for the melt-quenched sample. A decrease of 1 K in the glass relaxation temperature and 0.5 kcal (a at)^?1 in the activation energy was observed in samples which had been initially evaporated. No change was observed as a result of melting and quenching these evaporated samples.It is postulated that there was no change when the evaporated sample was melt-quenched be because rings and chains can interconvert and equilibrate relatively readily at temperatures as low as T_g (50° C), and consequently the samples all had the same structure after once being heated above T_g. The differences observed are probably due to accidental impurities in the evaporated samples which help catalyze the interconversion of rings and chains. Further, since the equilibrium concentration of polymeric chains is temperature dependent, it is postulated that the large relaxation effects seen at T < T_g are due to the equilibration of these chains with the rings. The observed activation energy for the relaxation supports this view. It is about the same energy as has been previously measured for Se₈ ring breaking in liquid selenium. Two consequences of this postulate are that the selenium analog to the sulfur polymerization transition must occur well below room temperature if it exists, and therefore, that the equilibrium ring-chain ratio can be smoothly extrapolated down to room temperature from the published high-temperature data.     

The Temperature Dependence of Electron Spin-Lattice Relaxation Data in Trans-Polyacetylene and the Evidence for a Soliton-Phonon Interaction

Abstract

The temperature and frequency dependence of the electron spin-lattice relaxation rate Rj for the paramagnetic defects in pristine transpolyacetylene is analyzed in terms of a model in which the electron-electron dipolar interaction between spins is modulated by one-dimensional diffusion induced by phonon scattering of the spins. According to this model, at room temperatures R₁ has a T¹/² temperature dependence; at low temperatures R₁ has a T² or T⁵/² temperature dependence. R₁ is described by a ω^?1/² frequency dependence. The model shows the symmetry between moving and stationary solitons scattered by phonons. The soliton wave function obtained from experimental ENDOR data is used to obtain analytical results. We discuss the possible temperature and frequency limitations of this model.     

Viscoelastic Parameters of a Side-Chain Nematic Polymer: I—Results of a Proton NMR Study

The reorientational behaviour in a static magnetic field of a nematic siloxane side-chain polymer is investigated by proton NMR. At variance with what occurs in main-chain and lyotropic nematic polymers, the return to equilibrium of a tnonodomain whose mean director has been rotated at an angle α to the field, is found to be homogeneous for all angles a between 0 and π/2. The usual nematic order parameter and the static (on the proton NMR time scale) order parameter are deduced from analysis of the equilibrium lineshapes. The twist viscosity γ₁ is deduced from the study of time dependent lineshapes following the rotations α. The temperature dependence of γ₁ is discussed in terms of the Vogel equation γ₁ = B S ^β exp(E _β/R(T - T _o}). It is not possible to discriminate between β = 1 or 2, but in both cases, the freezing temperature of the director T_o is found to be non-zero. A nematic to smectic pretransitional effect on γ₁ is observed. The information concerning the viscoelastic parameters contained in the value of the static order parameter is also discussed.     

Convective Temperature Fluctuations in Liquid Gallium in Dependence on Static and Rotating Magnetic Fields

The influence of static axial, static transversal, and rotating magnetic fields on convective temperature fluctuations in liquid gallium (temperature range around 800 °C, Prandtl number 2.5 · 10⁻³) has been investigated. For a Rayleigh number of 6.3 · 10⁻⁵ (ΔT = 10°C, h = 50 mm), convective temperature fluctuations with peak to peak values of 3 °C have been measured. Depending on the strength, the frequency, and the configuration of the field, they could be eliminated to ΔT < 0.01 °C (static axial field of 182 mT), damped to a nearly periodic state with 0.1 °C amplitudes (static transversal field of 45 mT), or reduced to 0.03 °C oscillations by applying a rotating field.     

In situ high temperature 27Al NMR study of structure and dynamics in a calcium aluminosilicate glass and melt

The temperature dependence (25–1400 °C) of ²⁷Al NMR spectra and spin–lattice relaxation time constants T₁ have been studied for a calcium aluminosilicate (43.1CaO–12.5Al₂O₃–44.4SiO₂) glass and melt using an in situ high temperature probe, and the glass has been characterized by ambient temperature, high field MAS NMR. The peak positions and the line widths show a consistent behavior as motional averaging of the quadrupolar satellites increases with increasing temperature. The rate of decrease with temperature of T₁ drastically increases near the glass transition temperature T_g, which suggests a change in NMR relaxation process from vibrational to translational motions. Above the T₁ minimum (≈1200 °C), NMR correlation times obtained from T₁ are in good agreement with shear relaxation times estimated from viscosity, suggesting that microscopic nuclear spin relaxation is controlled by the same dynamics as macroscopic structural relaxation, and thus that atomic-scale motion is closely related to macroscopic viscous flow.     

The two-step scenario of the protein dynamical transition

The “protein dynamical transition” (PDT) characterizes the abrupt loss of structural flexibility at a particular temperature and time scale in response to the glass transition of protein hydration water. The water-coupled structural degrees of freedom interact with the protein via hydrogen bonds, causing fluctuations, which can be probed by dynamic neutron scattering experiments. To emphasize the properties of hydration water a perdeuterated protein C-PC hydrated with H₂O is investigated together with native myoglobin. The respective intermediate scattering function of hydration water displays a two-step decay involving fast local re-orientational fluctuations and a slow collective relaxation. The anharmonic onset in the mean squared displacements, which is generally used to identify the PDT, is derived from the properties of the intermediate scattering function at the time given by the resolution of the spectrometer. It is shown that the onset temperature depends on the shape of the relaxation time spectrum. A shape-independent transition temperature T_Δ is defined, associated with the main structural relaxation, which decreases with increasing resolution. A second onset is identified near the glass temperature T_g, which is related to the initial decay of the intermediate scattering function. This onset is independent of the instrumental resolution and causes a change in molecular elasticity and thermal expansion. With this approach a more precise definition of the PDT is given, providing answers to the critical questions about the nature and the mechanism of the effect.     

Dielectric spectroscopy of low-losses sugar lyophiles: III: The influence of moisture on the dielectric response of freeze-dried lactose

This paper presents the results of a dielectric spectroscopy study of freeze-dried lactose with a range of moisture contents. Dielectric properties were measured over a wide range of frequency (10⁻¹ to 10⁶ Hz) and temperature (−120 °C to 120 °C). Four relaxation processes were analysed with respect to moisture content and corresponding relaxation mechanisms were suggested. Two processes (γ and β) were observed in the sub-T_g range of temperature and another two processes were observed near to and above the glass transition temperature, T_g. The relatively high-frequency γ-process was ascribed to the mobility of pendant hydroxymethyl groups and exhibited only a weak dependence on moisture content. The most moisture sensitive process was the second sub-T_g (Johari-Goldstein) β-process, whereby the relaxation time changed by 2 orders of magnitude as the moisture was increased by 7%. Also the third process (α-relaxation, near T_g) was sensitive to moisture content and was in good agreement with DSC data measured for freeze-dried lactose. The fourth process was a proton percolation process at the micro-crystals formed at the surface of amorphous particles during heating at the temperatures higher than T_g and shows the moisture dependence.     

Overhauser Shift of the Conduction Electron Spin Resonance in (FA)2PF6 Single Crystals

The shift ΔB _ov of the ESR line due to saturation of the NMR of the hyperfine coupled nuclei (Overhauser shift) was measured for single crystals of the organic conductor (FA)₂PF₆. ΔB_ov , is proportional to [Abar] _tt , being the average hyperfine interaction between the conduction electrons and the protons in resonance, and the dynamic nuclear spin polarization (DNP), respectively. The DNP enhancement factor V was determined for the two orientations of the static magnetic field B _o , perpendicular (V _∥ = 525 ± 40) and parallel (V _∥ = 280 ± 25) to the needle axis a, respectively. The absolute value of the average hyperfine coupling is [Abar]^zz = –(1.16 ± 0.05) Gauss · g_e μ _B . Both, the temperature dependence and the anisotropy of the proton spin relaxation times T ₁ ^p and T ₁ ^p were measured from the time dependence of the Overhauser shift, ΔB_ov (t) after rf-pulses or after switching “on” and “off” the ESR saturation. Within the metallic phase of the crystal the proton relaxation is governed by a Korringa law. The experiments definitely show, that the electron spins, showing up in the ESR are those of the conduction electrons.     

Modification of Fluid Flow and Heat Transport in Vertical Bridgman Configurations by Rotating Magnetic Fields

Applying a rotating magnetic field to an electrically conducting liquid, a Lorentz force is induced which generates a melt rotation of a certain angular velocity. A cylindrical gallium melt (aspect ratio 2.5) has been used as a model liquid. The melt has been heated from the bottom (Ra = 10⁶) or from the top (Ra = −10⁶) and the resulting temperature fluctuations in the melt have been measured in dependence on the rotating field strength (B_max = 30 mT). In the case of the unstable gradient 0.8 mT are sufficient to dominate the buoyancy driven convection and to reduce the amplitude of the buoyancy caused temperature oscillations for more than one order of magnitude. At the same time, the fluctuation frequency increases with the field strength. In the case of the stabilizing temperature gradient, low amplitude/high frequency temperature fluctuations are generated by the rotating magnetic field, indicating the transition to a time-dependent flow. In both cases we see an increase of the convective heat transport for magnetic inductions higher than approximately 5 m T. Applying the rotating magnetic field to the Bridgman growth of gallium doped germanium, the same behavior can be seen: Growing with a top-seeded arrangement, the intensity of the dopant striations is decreased and their frequency is increased. Growing with a bottom-seeded arrangement, the interface curvature changes from concave to convex and the flow becomes time-dependent.