The concentration dependence of the proton chemical shift and the deuterium quadrupole coupling parameter for binary solutions of ethanol

Concentration dependent experimental measurements of the ethanol hydroxyl proton chemical shift σ_H for binary solutions were carried out. The solvents used were carbon tetrachloride (CCl₄), benzene, chloroform, acetonitrile, acetone and dimethylsulphoxide (DMSO). The chemical shift values range from 0.69 ppm (relative to TMS) for dilute ethanol (extrapolated to infinite dilution) in CCl₄ to 5.34 ppm for neat liquid ethanol. Ab initio calculations of the ethanol-solvent hydrogen bond energies show a correlation with the values for the chemical shift. The hydrogen bond energies for ethanol-solvent dimers range from 0.63 kcal mol^?1 for ethanol-CCl₄ to 9.34 kcal mol^?1 for ethanol-DMSO. Theoretical calculations show a linear correlation between the deuterium quadrupole coupling parameter XD ^ar d the isotropic proton chemical shift σ_H: X_D(kHz) = 291.48 ? 14.96 σ_H, where σ_H is the proton chemical shift in ppm relative to TMS (R ² = 0.99). Using the concentration dependent chemical shift data and this equation, X_D ia observed to range from 280 kHz for very dilute concentrations in CCl₄, where the primary species is ethanol monomer, to 210 kHz for the neat liquid that is comprised primarily of cyclic pentamers.     

Dynamical structure of α-Ag0.99Cu0.01I crystal by Cu NMR chemical shift, spin-lattice relaxation time and molecular dynamics simulation

Solid ⁶³Cu NMR and Molecular Dynamics (MD) methods have been used to investigate the dynamical structure of Ag_0.99Cu_0.01I crystal, through the viewpoint of the chemical shift and the spin-lattice relaxation. In the superionic phase (α-phase), we obtained the temperature variation of the chemical shift as −0.2 ppm/K, and the activation energy of the Cu⁺ ion diffusion as 11 kJ/mol. The temperature dependence of the chemical shift was explained by the calculated chemical shielding surface based on ab initio MO calculation, and by the probability density of Cu⁺ ion estimated by MD simulation. The spin-lattice relaxation was also analyzed by using the MD method in which we assumed two jumping models as the diffusion process of the mobile cations. It is concluded that the temperature dependence of the chemical shift is dominated by the shielding in the vicinity of the 24(h) site, and the observed activation energy is due to the diffusion process of the mobile cations jumping from the 6(b) intrasub-lattice to the nearest-neighbor 6(b) sub-lattice.     

热致液晶CPHOB的有序参数与核磁共振弛豫

从室温至380K测量了热致液晶4-己氧基苯甲酸4-氰基苯酯（CPHOB）的氢核磁共振谱．其固态至向列相的转变温度T_sn=347K，向列相至各向同性液体的转变温度T_ni=359K．得到了液晶态有序参数的温度关系．讨论了氢核磁共振的自旋晶格弛豫机制． 关键词：     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Muon knight shift in platinum and in β-PdHx (x=0.70, 0.75, 0.86)

The ⁺ Knight shift in Platinum has been measured between 20 K and 785 K. It shows a strong temperature dependence and scales with the magnetic bulk susceptibility. A temperature independent contribution of +53±15 ppm and a d-electron induced hyperfine field per unpaired d-electron per atom of B _hfd ^a =–5.03 kG(±8.5%) are obtained. The ⁺ Knight shift in PdH_0.70, PdH_0.75 and PdH_0.86 shows no dependence on temperature between 20 K and RT and increases from K=–(8±3) ppm for x=0.70 to K =+(6.5±3) ppm K=+(6.5±3) ppm for x=0.86, in good agreement with proton Knight shift measurements.     

Reaction field model with free volume for the NMR chemical shift of129Xe dissolved in organic solvents

The temperature dependence of the NMR chemical shift of¹²⁹Xe dissolved in liquid alkanes is examined in the context of the reaction field model. An essential feature of the theory is the inclusion of the temperature dependence of the density of thesolvent. The theory of free volume for liquids is incorporated into the reaction field model to account for this temperature dependence. Comparison of the theory with previously reported measurements indicates the sensitivity of the¹²⁹Xe chemical shift to the free volume of liquids. Incorporation of free volume improves the agreement between measurement and theory for branched alkane solvents, and resolves the origin of the 62 ppm intercept in the plot of reaction field as a function of¹²⁹Xe chemical shift for the n-alkanes.     

NMR studies on hydrogen bonding and proton transfer in Mannich bases

A review of studies on the ortho Mannich bases containing various substituents in the phenyl ring on the basis of¹H,¹³C and¹⁵N nuclear magnetic resonance (NMR) spectra in various solvents over the temperature range 110–298 K is presented. Some new results are also included. The data gathered so far show that there is some critical (inversion) range of ΔpK _a (= pK _a(NH⁺) − pK _a(OH)) in which the proton transfer equilibrium appears. This inversion range is well reflected in the behaviour of secondary deuterium isotope effect in¹³C NMR spectra. A strong temperature effect on the strength of hydrogen bonding should be emphasized. The¹H chemical shift for trichloroderivative increases from 13.5 at room temperature up to 17 ppm at 130 K when the proton is equally shared between the bridging atoms (¹ J(¹H,¹⁵N) = 30–40 Hz). The potential for the proton motion in such bridges is discussed taking into account the behaviour in the ultraviolet and infrared spectra. The role of dimerization in proton transfer equilibria is shown. In addition the rotation of OH groups involved in hydrogen bond formation and nitrogen pyramidal inversion was studied by the¹H dynamical NMR spectra.     

Nuclear quadrupole resonance of norephedrine

Toward searching for illegal drugs, we investigated the pulsed nuclear quadrupole resonance (NQR) response of ¹⁴N in (1R,2S)-(-)-norephedrine, based on the predictions of quantum chemical calculations. Two pairs of spectral lines (ν₊=3.089, 3.093 MHz and ν₋=2.594, 2.608 MHz) were observed despite its molecule structure having only a single nitrogen atom. This indicates that the molecular crystal has two nonequivalent nitrogen atoms in the unit cell. The temperature dependence of the NQR frequencies and relaxation properties were investigated for the purpose of accurate remote sensing of the drugs. The NQR frequency shift was approximately 0.23 kHz/K around room temperature. The spin-lattice relaxation and spin-phase memory times were 5.2–10.2 ms and 0.6–1.5 ms, respectively.     

Rb87 spin-lattice relaxation in RbMnF3

Nuclear spin-lattice relaxation rate measurements of Rb⁸⁷ in the isotropic antiferromagnet RbMnF₃ have been performed from 27 to 500°K. Both the high temperature value of the relaxation rate and its temperature dependence are well explained by a theoretical calculation essentially based on Moriya's theory.     

NMR spectral densities and two dimensional diffusion in TiS2(NH3)1.0 and TaS2(NH3)x

NMR measurements of proton spin-lattice relaxation times T₁ and T_1? in the layered intercalation compounds TiS₂(NH₃)_1.0 and TaS₂(NH₃)_x (x = 0.8, 0.9, 1.0) are reported as functions of frequency and temperature (100 K – 300 K). These observations probe the spectral density of magnetic fluctuations due to motions of the intercalated molecules at frequencies accessible to the T₁ (4–90 MHz) and T_1? (1–100 kHz) measurements. Since the average molecular hopping time (τ) can be changed by varying temperature, different regions of the spectral density can be examined. For T > 200 K, both T^?1₁ and T^?1_1? vary logarithmically with frequency, reflecting the two dimensional character of the molecular diffusion. The temperature dependence of T₁ suggests that a more accurate picture of the short time dynamics is required. No dependence of relaxation rate on vacancy concentration is found.     

Photodynamics of intramolecular proton transfer in polar and nonpolar biflavonoid solutions

Using methods of steady state luminescence and femtosecond spectroscopy, we have studied the mechanism of intramolecular proton transfer in synthesized 3,7-dihydroxy-2,8-di(4-methoxyphenyl)-4H,6H-pyrano[3,2-g]chromen-4,6-dion in polar and nonpolar solutions, films, and polycrystals at 293 and 77 K. In an excited singlet state, intramolecular proton transfer occurs in two stages. At the first stage, a tautomer with one transferred proton (OTP tautomer) is formed from the Franck-Condon state within ??₁ = 0.6 ps. At the second stage, the second proton is transferred within ??₂ = 3.1 ps and a tautomer with two transferred protons (TTP tautomer) is formed, which fluoresces in toluene at 293 K with a high quantum yield, ?? _f = 0.66, and the fluorescence spectrum of which is characterized by a large Stokes shift, 9900 cm^?1. At 293 K, polar solvents (dimethylformamide, dimethyl sulfoxide, ethanol, etc.) solvate the BFV molecule in the ground state, while, in the excited state, an OTP tautomer is mainly formed. In polar ethanol at 77 K, a dual fluorescence spectrum is observed, which is caused by the fluorescence emission of polysolvates with ?? _max ^f = 460 nm and TTP phototautomers at ?? _max ^f = 610 nm.     

19F N.M.R. and 127I N.M.R. and N.Q.R. study of the molecular motions and deformations of iodine heptafluoride in its solid phases

In solid IF₇, ¹⁹F and ¹²⁷I N.M.R. and ¹²⁷I N.Q.R. absorption line shapes, frequencies and relaxation times have been studied from the melting temperature down to 56 K. Two new solid-solid transitions have been found at 180 K and 96 K in addition to the one already known at 153 K. The two high temperature phases are shown to be plastic. The fast molecular rotations and the slow molecular diffusion are studied from ¹⁹F and ¹²⁷I relaxation times. In the ordered phases, an analysis of the ¹⁹F second moments and longitudinal relaxation times shows the existence of a fast intramolecular exchange between axial and equatorial fluorine atoms, together with a much faster reorientation about the D ₅ axis. The characteristic times of these two motions are obtained and a mechanism for the exchange process is proposed. The chemical shift values of ¹²⁷I, the temperature dependence of the N.Q.R. frequencies and of the N.Q.R. relaxation times of ¹²⁷I, as well as the dipolar energy relaxation times have been measured and are discussed.     

Temperature-Dependent Solid-State 119Sn- MAS NMR of Nd2Sn2O7, Sm2Sn2O7, and Y1.8Sm0.2Sn2O7. Three Sensitive Chemical-Shift Thermometers

The ¹¹⁹Sn MAS NMR resonances of the paramagnetic stannates Ln₂Sn₂O₇ (Ln = Nd, Sm, and Y_1.8Sm_0.2) have been found to be extremely sensitive to temperature, the isotropic resonances varying, at room temperature, by 14 and 1.1 ppm K^−l for Nd₂Sn₂O₇ and Sm₂Sn₂O₇, respectively. This sensitivity has been exploited to develop three chemical-shift thermometers with reciprocal dependences on temperature. Sm₂Sn₂O₇ is suitable for temperature calibration of standard MAS probes and the solid solution Y_1.8Sm_0.2Sn₂O₇ is a shift thermometer with an internal reference. Nd₂Sn₂O₇ is proposed as a high-temperature shift thermometer. These thermometers were used to determine the changes in sample temperature, in a Bruker 7 mm double-bearing probe, as the MAS speed was varied. A change of 8.5 K was observed on increasing the MAS speed from 1 to 5 kHz. The short relaxation times of the ¹¹⁹Sn nuclei enabled short recycle times to be used, and spectra of Sm₂Sn₂O₇ could be obtained in seconds.     

NMR and magnetic studies on 7 K anomaly in Tl3H(SO4)2

Measurements of the spin-lattice relaxation time, NMR absorption line and magnetization have been carried out on the Tl₃H(SO₄)₂ crystal below 50 K. The anomaly at around 7 K was: (1) the spin-lattice relaxation times of ¹H and ²⁰⁵Tl nuclei increase steeply with decreasing temperature below 7 K, (2) the NMR absorption lines below 7 K shift to the high-magnetic field side in comparison with that above 7 K, and (3) the ¹H NMR line width exhibits a drastic increase of the line width with decreasing temperature below 7 K. These results indicate that the magnetic dipole fluctuation of the proton changes at 7 K. On the other hand, there are no remarkable anomalies of magnetic susceptibility at around 7 K. From these results it is deduced that the anomaly at around 7 K is caused by the change in quantum mechanical process of the proton from proton tunneling to zero-point vibration of hydrogen in the hydrogen bond with the decrease of temperature.     

H NMR study of the phase transitions of trissarcosine calcium chloride single crystals at low temperature

The ¹H NMR line-width and spin-lattice relaxation time T₁ of TSCC single crystals were studied. Variations in the temperature dependence of the spin-lattice relaxation time were observed near 65 and 130 K, indicating drastic alterations of the spin dynamics at the phase transition temperatures. The changes in the temperature dependence of T₁ near 65 and 130 K correspond to phase transitions of the crystal. The anomalous decrease in T₁ around 130 K is due to the critical slowing down of the soft mode. The abrupt change in relaxation time at 65 K is associated with a structural phase transition. The proton spin-lattice relaxation time of this crystal also has a minimum value in the vicinity of 185 K, which is governed by the reorientation of the CH₃ groups of the sarcosine molecules. From this result, we conclude that the two phase transitions at 65 and 130 K can be discerned from abrupt variations in the ¹H NMR relaxation behavior, and that ¹H nuclei play important roles in the phase transitions of the TSCC single crystal.     

Muon Knight shift in platinum and in β-PdHx (x=0.70, 0.75)

The ⁺ Knight shift in platinum has been measured between 20 K and 785 K. It shows a strong temperature dependence and scales with the magnetic bulk susceptibility. A temperature independent contribution of +40 to +60 ppm and a d-electron induced hyperfine field per unpaired d-electron per atom ofB _hf,d =–5.03 kG (±8.5%) are obtained. The ⁺ Knight shift in PdH_0.70 and PdH_0.75 shows no dependence on temperature between 20 K andRT and increases fromK ppm forx=0.70 toK ppm forx=0.75, in good agreement with proton Knight shift measurements.     

Dependence of NMR isotropic shift averages and nuclear shielding tensors on the internal rotation of the functional group X about the C-X bond in seven simple vinylic derivatives H2C=CH-X

The ‘Gauge Including Atomic Orbitals’ (GIAO) approach is used to investigate the question of intramolecular rotation. Ab initio GIAO calculations of NMR chemical shielding tensors carried out with GAUSSIAN 94 within the SCF-Hartree-Fock approximation are described. In order to compare the calculated chemical shifts with experimental ones, it is important to use consistent nuclear shieldings for NMR reference compounds like TMS. The influence of rotating functional groups X=CH₃, CHO, NO₂, NH₂, CONH₂, COOH or C₆H₅ on the shielding tensors in seven vinylic derivatives H₂C=CH-X is studied; the molecules are propene, acrolein, nitroethylene, ethyleneamine, acrylamide, acrylic acid and styrene. We observe a marked dependence of nuclear shielding and chemical shift on the torsional movement. Different Boltzmann averages over the conformational states are considered and compared for gas phase, liquid and solid state NMR. Their applicability to model cases for rigid or freely rotating molecules and for fixed molecules (e.g. polymers or proteins) with rapidly rotating groups is discussed and simple calculation models are presented. On the basis of this work it can be concluded that intramolecular rotation clearly affects the observed averages. Effects of up to 2 ppm have been observed for isotropic chemical shifts, and up to 17 ppm difference have been observed for individual tensor components, for example, of the carboxylic ¹³C atom in acrylic acid. The variation of the shielding tensor on a nucleus in a fixed molecular backbone resulting from an attached rotating group furthermore leads to a new relaxation mechanism by chemical shift anisotropy.     

Mössbauer studies related to the solid-state dynamics of C60

Summary C₆₀ (Buckminsterfullerene) is isolated from organic solvents above 260 K as an f.c.c. solid with complete orientational disorder. The rotational dynamics are diffuse and isotropic, with a short (12 ps) correlation time at 300 K. Below 260 K, the solid forms in a simple cubic lattice withPa3 symmetry. The librational motion occurs by activated jumps with a correlation time of about 60 ns at 200 K. To gain further insight into the dynamics of C₆₀, the compound C₆₀Fe(CO)₄ (I) (generously made available to us by A. Stephens and M. Green of Oxford University) has been studied by⁵⁷Fe M?ssbauer spectroscopy. As expected, the resonance at 90 K consists of a doublet with an isomer shift (relative to metallic iron) of 0.034(1) mm s⁻¹ and a quadrupole splitting of 1.607(5) mm s⁻¹. There is no significant temperature-dependent, intensity asymmetry of the doublet. The temperature dependence of the effect magnitude is well fit by a linear regression over the range 85<T<210 K. To elucidate the relationship of these results to the effect of the C₆₀ moiety in I, further lattice dynamical M?ssbauer studies have been carried out on (maleic anhydride) Fe(CO)₄ (II), one of the few isolatable tetracarbonyl complexes of iron. For (II), the quadrupole splitting is 1.371(5) mm s⁻¹ at 90 K, and the temperature, dependence of the isomer shift is smaller than it is for (I), while the temperature dependence of the recoil-free fraction is significantly larger in (I) than in (II). Paper presented at ICAME-95, Rimini, 10–16 September 1995.     

High temperature behavior of the chemical shift and nuclear spin relaxation of Se77 in solid selenium

The spin-lattice relaxation and the chemical shift (CS) anisotropy of Se⁷⁷ in selenium single crystals have been investigated between room temperature and the melting point (490 K). Over the entire temperature range, the CS-anisotropy is shown to be independent of the temperature. The temperature dependence of the spin-lattice relaxation is determined by phonon-induced fluctuation of the CS-tensor. Above 400 K, translational atomic diffusion causes a remarkable additional increase in the relaxation rate.     

Magnetic studies with μSR at high pressures

A newly developed high pressure-low temperature μSR spectrometer was employed for two types of magnetic studies. Firstly we measured the pressure dependence of the local magnetic field B_μ in Fe, Co and Ni at 77 K up to 7 kbar. From the pressure derivative dlnB_μ/dP the volume derivative dlnB _Hf /dlnV was deduced. In connection with previous room temperature data we calculated the temperature dependence of B_hf at constant volume. It deviates markedly from the temperature dependence of the host magnetization. Secondly, we looked at the pressure dependence of the muonic Knight shift in Sb at 30 K for polycrystalline and single crystal samples. A strong pressure dependence was observed which depends on the orientation of the magnetic field relative to the c-axis. The pressure coefficients of the isotropic and the axial term of the Knight shift were deduced.