Molecular reorientation and phase transition in pyridinium hexafluoroantimonate

The temperature dependence of ¹H and ¹⁹F NMR second moment and spin lattice relaxation times in high (v _L = 60 MHz and low (B ₁ = 2 mT) magnetic fields allow one to determine both ion dynamics in polycrystalline pyridinium hexafluoroantimonate. The solid-solid phase transition discovered at 268 K appears to be connected with symmetrization of energy barriers for pseudohexagonal cation reorientation. The energy difference Δ characterizing the inequivalence of the potential wells can be treated as an order parameter. The effect of coupling of the rotational modes of cations and anions is found at the phase transition.     

Pressure Effect on Molecular and Lattice Dynamics in Pyridinium Nitrate

Measurements of spin-lattice relaxation time T 1 , second moment M 2 and neutron scattering have been performed for a polycrystalline sample of pyridinium nitrate as a function of hydrostatic pressure and temperature. The structure of this compound has also been analysed by the HF/6-31 G method. The results of the measurements and calculations have confirmed that reorientation of the pyridinium cation takes place between the potential minima of different values, and the asymmetry parameter decreases with increasing temperature. The temperature dependence of the asymmetry parameter is modified by the pressure applied. The presence of the hydrogen bond in this compound implies a very small activation volume and is responsible that the crystal does not undergo a phase transition to the disordered phase.     

NMR studies of cation transport in the crystalline ion conductors MCF3SO3 (M = Li,Na) and Li7TaO6

In this contribution we present studies on the mechanism of ion transport in crystalline solid electrolytes employing a range of different solid state nuclear magnetic resonance (NMR) experiments. The first part is devoted to the elucidation of a possible correlation of cation transport and anion reorientation in the dynamically disordered rotor phases of alkali trifluoromethane sulfonates MCF₃SO₃ (M = Li, Na) employing ⁷Li, ¹³C, ¹⁷O and ²³Na NMR line shape analysis, whereas the second part focuses on the tracking of cation diffusion pathways in the hexaoxometalate Li₇TaO₆ utilizing ⁶Li 1D and 2D exchange MAS NMR approaches.     

High pressure study of cation dynamics in pyridinium Perchlorate

Measurements of spin-lattice relaxation time and complex permittivity have been performed for monocrystalline and polycrystalline pyridinium Perchlorate as a function of hydrostatic pressure and temperature. The influence of pressure on the reorientation of the pyridinium cation was analysed. The potential shape and heights of the energy barriers for this reorientation in all three phases have been determined. For phase I and III the pressure dependence of the activation enthalpy was obtained.     

A 2H and 14N NMR study of molecular motion in polycrystalline choline salts

²H and ¹⁴N solid-state NMR spectra of polycrystalline choline chloride, bromide, and iodide indicate that 180° cation flipping motion occurs in all three salts. From the temperature dependence of these spectra, the activation energy for this motion is determined to be 5.8 ± I kcal/mol in the iodide salt and 11 ± 1.5 kcal/mol in the chloride salt. In the bromide salt the reorientation rate is too rapid to be determined from the NMR lineshape, but the temperature dependence of the ²H quadrupole coupling parameters is indicative of a second-order phase transition at approximately 273 K. The spectral distortions in the ¹⁴N NMR spectra of the chloride and iodide salts are adequately explained using the motional model derived from the ²H NMR results, while the ¹⁴N spectra of the bromide salt show no motional effects. The axis of reorientation which is inferred from these data appears to be consistent with that indicated in a previous X-ray crystallographic study.     

Proton-irradiation effect on the proton motion in TlH2PO4

We have investigated the proton-beam irradiation effect on TlH₂PO₄ (TDP) undergoing an antiferroelectric phase transition and a ferroelastic one. The polycrystalline sample was irradiated by a 1 MeV hydrogen ion beam to a dose of 10¹⁵ ions/cm². The changes in the ¹H nuclear magnetic resonance (NMR) line shapes are discussed in view of the two distinct proton motions, which were identified from the line shape analysis, exhibiting contrasting behaviors after the proton-irradiation.     

<Superscript>1</Superscript>H and <Superscript>19</Superscript>F NMR relaxation time studies in (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> superionic conductor

¹H and ¹⁹F spin-lattice relaxation times in polycrystalline diammonium hexafluorozirconate have been measured in the temperature range of 10–400 K to elucidate the molecular motion of both cation and anion. Interesting features such as translational diffusion at higher temperatures, molecular reorientational motion of both cation and anion groups at intermediate temperatures and quantum rotational tunneling of the ammonium group at lower temperatures have been observed. Nuclear magnetic resonance (NMR) relaxation time results correlate well with the NMR second moment and conductivity studies reported earlier.     

NMR study of guanidinium cation dynamics in C(NH2)3SbCl6

Proton NMR second moment and spin—lattice relaxation times T ₁ and T _1p have been studied for polycrystalline guanidinium hexachloroantimonate C(NH₂)₃SbCl₆ in a wide temperature range. A dynamic inequivalence of two cations has been detected in spite of their crystal-lographical equivalence. Activation parameters for C₃ reorientation and self-diffusion of the more mobile cation have been determined. It was shown that the para–ferroelastic phase transition at 351 K is connected with abrupt changes in the dynamics of the two cations. The weaker, second-order transition at 265 K is thought to be related to a change in the dynamics of one of the cations.     

Quadrupole interactions in lithium borodeuteride

Polycrystalline samples of lithium borohydride and borodeuteride, LiBH₄ and LiBD₄, are studied by ²H, ⁷Li, and ^10,11B NMR in 7.04 T and 9.35 T magnetic fields in the temperature range 116–580 K. The ^10,11B NMR line shape of the orthorhombic phase of LiBH₄ and LiBD₄ suggests that first-order quadrupole interaction takes place. The quadrupole coupling constant (QCC) χ _q and asymmetry parameter η of the electric field gradient tensor for ¹¹B are described by linear temperature dependences: χ _q (¹¹B) = 177 ? 0.24T and η = 0.043 + 0.0014T. The electric field gradient at the positions of boron nuclei is created by external charges, primarily lithium cations. In the range of 388–391 K, the ⁷Li NMR line shape reflects the coexistence of two phase modifications of LiBH₄ and LiBD₄ and the occurrence of a reversible first-order phase transition. In the temperature range of 390–530 K, the ⁷Li NMR line shape represents a first-order quadrupole perturbed spectrum with zero asymmetry parameter and a weakly temperature dependent ⁷Li QCC. The spin-lattice relaxation time and the NMR line shape of ²H are interpreted in terms of the reorientation of the BD ₄ ^? anion about their proper symmetry axes C₂ and C₃.     

<Superscript>2</Superscript>H and <Superscript>47, 49</Superscript>Ti nuclear magnetic resonance in the γ phase of titanium deuterides TiD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Titanium deuterides TiD_1.92, TiD_1.98, and TiD_2.0 have been studied by ²H and ^{47, 49}Ti NMR in a magnetic field of 7.04 T and a temperature range of 120–500 K. At all temperatures and compositions, the ²H NMR line is a singlet described by the Gaussian function. The contribution of demagnetizing fields to the ²H NMR shift is ∼50 ppm. The titanium NMR spectra for all compositions comprise two signals due to the ⁴⁷Ti and ⁴⁹Ti isotopes. The shift between these signals depends on the deuterium content and temperature. The ^{47, 49}Ti NMR line shape, width, and shifts have been considered in the framework of second-order quadrupole effects for a tetragonal lattice distortion and random distribution of vacancies. The Knight shifts σ(²H) and K(^{47, 49}Ti) are a function of temperature with a clearly pronounced singularity at ∼300 K. The contact, orbital, and polarization contributions to the Knight shifts have been estimated from analysis of the temperature dependences of σ(²H) and K(^{47, 49}Ti).     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Spin reorientation in Er2Fe17−xMnx - Mössbauer effect study

The polycrystalline samples of Er₂Fe_17–xMn_x compounds have been studied by⁵⁷Fe Mossbauer spectroscopy in the temperature range between 4.2K and 200K. A reorientation of the easy axis of magnetization has been evidenced for compound with x=4 in the measurements on magnetically oriented powdered sample. Spin reorientation from the c-axis to the basal plane is observed when temperature is increased above 105K.     

Phase transitions and127I,133Cs quadrupole couplings in polycrystalline Cesium metaperiodate

The¹²⁷I and¹³³Cs NMR spectra of polycrystalline CsIO₄, a material of potential interest for transformation of laser irradiation, have been measured in the temperature range 170–440 K and the line shape has been analyzed taking into account first and second order quadrupole interactions and chemical shift anisotropy. Quadrupole coupling constants and asymmetry parameters have been determined as a function of temperature.¹²⁷I and¹³³Cs data consistently show two phase transitions in the ranges 243–300 K and 420–440 K with a temperature hysteresis for the first transition and a range for coexistence of two phases. The time evolution of the NMR signal suggests the existence of piezomagnetism, which was believed to exist only in crystals with a magnetic structure.     

Fluorine NMR in Zirconium,Hafnium and Thorium Tetrafluorides and f-Orbital Contribution to Interatomic Bonds

Previously¹ we have observed a ¹⁹ NMR asymmetric line in polycrystalline ThF₄ in the 6–9 kOe fields, which was ascribed to the anisotropy of the ¹⁹F nuclei screening constant. However, the accepted interpretation in the case of a powder sample is not the only possible one, since in the presence of chemically or structurally non-equivalent fluorine atom groups spectrum asymmetry may also arise on account of the difference in the nuclei magnetic screening constants due to non-equivalent positions. This dilemma in the case of polycrystalline samples may be solved only when recording spectra in the highest fields. Non-equivalence of the nuclei may lead, to a split of the NMR spectrum into components, corresponding to the various positions. When spectrum asymmetry is due to the anisotropy of the screening constant, field strength rise may but lead to an increase of the total spectrum width, its shape remaining unaltered.     

63Cu and65Cu Fourier transform nuclear magnetic resonance studies

⁶³Cu and⁶⁵Cu NMR studies are reported in liquid and solid copper (I) compounds. Ratios ofg _I-factors, nuclear magnetic moments and nuclear magnetic shielding constants in the atomic reference scale are given for⁶³Cu and⁶⁵Cu in a solution of Cu(I)(CH₃CN)₄BF₄ in CH₃CN, which is a reasonable reference sample due to the relatively narrow NMR line.     

A Definitive Example of Aluminum-27 Chemical Shielding Anisotropy

Solid-state²⁷Al NMR spectra have been obtained for a crystalline 1:1 complex of AlCl₃and OPCl₃. Aluminum chloride phosphoryl chloride, AlCl₃· OPCl₃(1), is unusual in that the Al–O–P bond angle is close to 180°. From analysis of the²⁷Al MAS NMR spectra, it was determined that the²⁷Al nuclear quadrupole coupling constant is 6.0(1) MHz, the asymmetry in the electric field gradient (efg) tensor is 0.15(2), and the isotropic chemical shift, δ_iso(²⁷Al), is 88(1) ppm. Solid-state²⁷Al NMR of a stationary sample reveals a line shape affected by a combination of anisotropic chemical shielding and second-order quadrupolar interactions. Analysis of this spectrum yields a chemical shift anisotropy of 60(1) ppm and orientations of the chemical shift and electric field gradient tensors in the molecular frame. Experimental results are compared with those calculated usingab initioHartree–Fock and density functional theory.     

Nuclear magnetic resonance study of potassium dihydrophosphate

A powder sample of potassium dihydrophosphate KH₂PO₄ has been studied by the ³¹P NMR method in a wide temperature range covering the ferroelectric phase transition. Changes in the position and shape of the resonance line at the transition to the ferroelectric phase have been revealed. The parameters of the chemical shift tensor of ³¹P (isotropic shift, anisotropy, and asymmetry) in the ferroelectric phase have been calculated from the experimental data. A sharp increase in the anisotropy of the tensor at the phase transition has been demonstrated. Dielectric measurements have also been carried out to verify the transition temperature.     

<Superscript>1</Superscript>H NMR study of molecular dynamics of acetylcholine chloride

The longitudinal relaxation timeT ₁ and the second momentM ₂ of¹H nuclear magnetic resonance line in a wide temperature range have been measured for acetylcholine chloride. Two different types of the methyl groups reorientation occurred. The first type was the hindered rotation of the methyl group denoted as C(1)H₃ about the threefold symmetry axis. The second type was the reorientation of the trimethyl group-N(CH₃)₃ around the pseudo C₃^′ axis of C(6)-N(7) bond, which accompanied the standard C₃ motion of the methyl group. The Dunn-McDowell model was applied to analyze the dynamics observed.     

CH3NH3 + as a quantum and classical rotor

Spin-lattice relaxation time T ₁ is determined for protons in three polycrystals (CH₃NH₃)₅Bi₂Cl₁₁, (CD₃NH₃)₅Bi₂Cl₁₁ and (CH₃ND₃)₅Bi₂Cl₁₁. The temperature dependence of the relaxation times obtained for (CH₃NH₃)₅Bi₂Cl₁₁ and (CD₃NH₃)₅Bi₂Cl₁₁ are interpreted as a result of correlated motions of the three-proton groups of the monomethylammonium cation. ²H NMR lines of (CD₃NH₃)₃Sb₂Br₉ have been recorded between 5 K and 291 K using solid echo method. The ²H NMR line shape analysis shows that characteristic shape of tunnelling methyl group appears at about 25 K and coming down with temperature up to 5 K is more distinct. From theoretical calculation, it has been found that in the quadrupolar constants is 161.3 kHz and tunnelling frequency is above 3 MHz.