35Cl NQR studies of 1‐chloro‐2,4‐dinitrobenzene and 1,2‐dichloro‐3‐nitrobenzene as a function of pressure and temperature

The temperature and pressure dependences of ³⁵Cl nuclear quadrupole resonance (NQR) frequency and spin–lattice relaxation time (T₁) were investigated for 1‐chloro‐2,4‐dinitrobenzene and 1,2‐dichloro‐3‐nitrobenzene. T₁ was measured in the temperature range 77–300 K. Furthermore, the NQR frequency (ν) and T₁ for these compounds were measured as a function of pressure up to 5.1 kbar at 300 K. Relaxation was found to be due to the torsional motion of the molecule and the reorientation motion of the nitro group. By analysing the temperature dependence of T₁, the activation energy for the reorientation motion of the nitro group was obtained. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities W₁ and W₂ for the Δm = ±1 and Δm = ±2 transitions, were also obtained. Both compounds showed a non‐linear variation of NQR frequency with pressure. The pressure coefficients were observed to be positive. A thermodynamic analysis of the data was carried out to determine the constant‐volume temperature coefficients of the NQR frequency. The spin–lattice relaxation time T₁ for both the compounds was found to be weakly dependent on pressure, showing that the relaxation is mainly due to the torsional motions. Copyright © 2002 John Wiley & Sons, Ltd.     

Temperature‐ and pressure‐dependent study of 35Cl NQR frequency and spin lattice relaxation time in 2,3‐dichloroanisole

The temperature and pressure dependence of ³⁵Cl NQR frequency and spin lattice relaxation time (T₁) were investigated in 2,3‐dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T₁ were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation of motion of the CH₃ group. T₁ versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH₃ group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules. Copyright © 2010 John Wiley & Sons, Ltd.     

35Cl NQR frequency and spin lattice relaxation time in 3,4‐dichlorophenol as a function of pressure and temperature

The pressure dependences of ³⁵Cl nuclear quadrupole resonance (NQR) frequency, temperature and pressure variation of spin lattice relaxation time (T₁) were investigated in 3,4‐dichlorophenol. T₁ was measured in the temperature range 77–300 K. Furthermore, the NQR frequency and T₁ for these compounds were measured as a function of pressure up to 5 kbar at 300 K. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities W₁ and W₂ for the Δm = ±1 and Δm = ±2 transitions were also obtained. A nonlinear variation of NQR frequency with pressure has been observed and the pressure coefficients were observed to be positive. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. An attempt is made to compare the torsional frequencies evaluated from NQR data with those obtained by IR spectra. On selecting the appropriate mode from IR spectra, a good agreement with torsional frequency obtained from NQR data is observed. The previously mentioned approach is a good illustration of the supplementary nature of the data from IR studies, in relation to NQR studies of compounds in solid state. Copyright © 2012 John Wiley & Sons, Ltd.     

Pressure and temperature dependence of the chlorine NQR in caesium and sodium chlorates

The (35)Cl nuclear quadrupole resonance (NQR) frequencies (nu(Q)) in caesium and sodium chlorates were measured as a function of temperature, from 77 to 300 K at different pressures up to 5.1 kbar, and the data were analysed to estimate the volume dependence of the electric field gradient (EFG), torsional frequency and also the contributions to the NQR frequency from static and dynamic effects. The variation of spin-lattice relaxation time with pressure at different temperatures was studied in the case of sodium chlorate and at room temperature in case of caesium chlorate. The pressure dependence of the spin-lattice relaxation time (T(1)) suggests that the relaxation is mainly due to the torsional motions.     

Nuclear quadrupole resonance in 2,4-dinitrochlorobenzene

A study of the spin lattice relaxation (T₁) and the nuclear quadrupole resonance frequency (ν_Q) gives an important information about the dynamics of molecular groups in molecular solids. In the present paper, we analyze the contributions of the reorientational motion of nitro groups of 2,4-dinitrochlorobenzene to the NQR parameters of the chlorine nucleus in the molecule.

We found two contributions to T₁ and ν_Q due to the onset of the reorientation of nitro groups in the molecule; one of these contributions is mostly due to intermolecular effects in the crystal. For the chlorine nuclei, the efficiency of the modulation mechanism is usually provided by the change of the electric field gradient due to the moving molecular group; this gives us a way of how to assign each contribution to T₁ from the ortho and para positions of the NO₂ groups in the molecule. It is observed that there are two different potential barriers depending on the position of the nitro groups in the molecule. The behavior in the temperature dependence of the line width shows a thermal history dependence of the molecular crystal.     

N NQR in the tetrazole family

¹⁴N NQR frequencies and spin–lattice relaxation times were measured in technologically important 5-aminotetrazole and 5-aminotetrazole monohydrate at different temperatures between 77 K and 300 K. Five NQR triplets ν₊, ν₋ and ν₀ were found for the five inequivalent nitrogen atoms in each compound between 0.7 MHz and 4 MHz. Carr-Purcell based multipulse sequences were used to accumulate quadrupole echo signals before the FFT analysis. Assignment of the frequencies to atomic positions was made and the results are analysed in relation to the molecular chemical bonds and possible H-bonds in the crystal structures. The new NQR frequencies are reasonably related to the previously published NQR spectrum of the third family member, 1H-tetrazole.     

35Cl Nuclear Quadrupole Resonance and Thermally Activated Molecular Motion in the 2:1 Crystalline Complex of Antimony Trichloride with Benzene

Nuclear quadrupole resonance (NQR) spectra of chlorine and antimony in the 2SbCl₃ · C₆H₆ complex and their temperature behavior between 77 K and the melting point were studied. The spectral lines of two nonequivalent SbCl₃ moieties are compared with available Xray diffraction data. An analysis of the temperature dependence of the resonant frequency and the spin–lattice relaxation time for ³⁵Cl nuclei showed the existence of thermally activated, intramolecular motion of chlorine atoms in this complex. The nature of the motion is determined by the shape of the SbCl₃ moieties. The activation energies of the motion were obtained for the two structurally nonequivalent halves of the complex (75.5 and 79.5 kJ/mole).     

Nuclear magnetic resonance study of Li and H diffusion in the high-temperature solid phase of LiBH4

In order to study the atomic jump motions in the high-temperature solid phase of LiBH₄, we have measured the ¹H and ¹¹B nuclear magnetic resonance (NMR) spectra and the ¹H, ⁷Li and ¹¹B spin–lattice relaxation rates in this compound over the resonance frequency range of 14–34.4 MHz. In the temperature range 384–500 K, all the spin–lattice relaxation data are satisfactorily described in terms of a thermally activated jump motion of Li ions with the pre-exponential factor τ₀=1.1×10⁻¹⁵ s and the activation energy E_a=0.56 eV. The observed frequency dependences of the spin–lattice relaxation rates in this temperature range exclude a presence of any distributions of the Li jump rate or any other jump processes on the frequency scale of 10⁷–10¹⁰ s⁻¹. The strong narrowing of the ¹H and ¹¹B NMR lines above 440 K is consistent with the onset of diffusive motion of the BH₄ tetrahedra.     

Pressure variation of C1 NQR in hexachlorostannate crystals

The effect of hydrostatic pressure (0 < p < kbar) on the ³⁵Cl NQR in K₂SnCl₆, (NH₄)₂SnCl₆, Rb₂SnCl₆ and Cs₂SnCl₆ was studied in the temperature range 20 K to 450 K. In the cubic phase the linear pressure coefficients of the NQR frequency ν_Q are negative. The frequency shifts are discussed in the scope of a microscopic model considering the variation of the static and dynamic part of the electric field gradient (EFG).On applying pressure the relaxation rate T₁^?1 decreases. At elevated temperature this pressure behaviour is attributed to the increase of the enthalpy of activation of the SnCl₆^2? motion. For K₂SnCl₆ the volume of activation ΔV_a could be estimated from the T₁^?1(P,T) data. Using this value a barrier height to rotation of ΔE_a = 4800 K is obtained.     

Mobility of CD4 molecules in nanoscale cages of zeolites as studied by deuteron NMR relaxation

Deuteron spin–lattice relaxation was applied to study mobility of CD₄ molecules trapped in the cages of zeolite NaY. There are two, interconnected sets of cages: α-cages and β-cages with 1.16 and 0.74 nm diameter, respectively. The relaxation temperature dependence, measured between 4 and 300 K, can be divided into four ranges with characteristic motional parameters. At higher temperatures exchange between cages dominates. Increasing rate of translational motion leads to a significant reduction of the relaxation rate. Features typical for quantum rotors were observed at low temperatures. Molecules in the α-cages exhibit reorientational freedom, while motion of these in β-cages is significantly restricted. Increasing abundance of molecules in β-cages indicates slow diffusion down to low temperatures.     

New polynuclear 4,4ˈ-bis-1,2,4-triazole Fe(II) spin crossover compounds

Two novel polynuclear Fe(II) spin crossover materials of formula 〚Fe(btr)₃〛 〚Fe(btr)₂(H₂O)₂〛(anion)₄, where btr = 4,4′-bis–1,2,4-triazole and anion = BF₄^–, PF₆^–, have been prepared and their spin transition characteristics studied over the temperature range 5–300 K. They both reveal incomplete spin crossover behaviour. Two different Fe(II) lattice sites of the FeN₆ and FeN₄O₂ type are distinguished by ⁵⁷Fe Mössbauer spectroscopy. The first site is responsible for the SC behaviour whereas the second one remains high-spin throughout the whole temperature range. This explains why it is not possible to switch all the Fe(II) ions to the low-spin state by application of hydrostatic pressure for the BF₄^– derivative. The temperature dependence of the population of these sites has been carefully analysed by Mössbauer spectroscopy.     

Disorder in condensed matter systems: proton spin lattice relaxation study of the mixed systems of betaine phosphate and glycine phosphite, BPxGPI(1-x)

Proton NMR relaxation measurements have been carried out in the mixed system of antiferroelectric (AFE) betaine phosphate (BP) and ferroelectric (FE) glycine phosphite (GPI), BPxGPI(1-x), at 11.4 and 23.3 MHz from 300 to 100 K for x=0.3, 0.4, 0.5, 0.6, 0.7 and 0.8. The temperature dependence of spin lattice relaxation (SLR) time follows the BPP model in the parent compounds, while the Larmor frequency dependence of T1 in the mixed system is rather unusual. The T1 curve exhibits different slopes for the low-temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (Ea), indicating disorder. For x=0.3 and 0.4, biexponential recovery of magnetization has been observed below 190 K, showing that the degree of disorder varies with the concentration. The temperature dependence of relaxation time data has been interpreted in terms of NH3, trimethyl ammonium and methyl group reorientations.     

Spectroscopic investigations of phase transition in 5-chloro-2-pyridone

Spectroscopic investigation of 5-chloro-2-pyridone has been carried out in the temperature range 77–300 K. At room temperature the ³⁵Cl NQR spectrum shows a single line at 35.618 MHz, but at 250.7 K two lines appear at 35.850 MHz and 35.840 MHz respectively indicating the presence of a phase transition. IR, far-IR, laser Raman and dielectric measurements have been carried out to investigate the phase transition further. Low temperature IR studies show splitting of ν(CCl), β(NH) and ν(CO) bands at T_c. Dielectric measurements show a small, but finite, change in the value of the dielectric constant around T_c. Raman spectra at different temperatures support the existence of a new phase, as shown by the appearance of a new band at 81 cm⁻¹, the frequency of which changes slowly as T_c is approached and which disappears at T_c. The temperature dependence of the NQR frequencies has been analysed using Bayer Kushida and Brown equations toevaluate the torsional frequencies.     

Nuclear spin relaxation dynamics of 13CO2 sorbed in polyisobutene rubber

Recently we presented the dynamics of ¹³CO₂ molecules sorbed in silicone rubber (PDMS) ascertained from spin relaxation experiments. Results of a similar investigation for ¹³CO₂ sorbed in polyisobutene (PIB) are presented in this report. The spin-lattice and spin-spin relaxation times as well as nuclear Overhauser enhancements (NOE) were determined as a function of temperature and Larmor frequency. The relaxation mechanisms found to be important for ¹³CO₂/PIB system are intermolecular dipole-dipole relaxation and chemical shift anisotropy with a minor contribution from spin rotation relaxation. We have determined the parameters which characterize correlation times for ¹³CO₂ collisional motion, rotational motion, and translational motions in the PIB. The self-diffusion coefficient of 5.15 × 10^?8 cm²/s obtained from the nuclear magnetic resonance (NMR) data is close to the literature value of the mutual diffusion coefficient of CO₂ in PIB at 300 K obtained from permeability measurements. In contrast to the case of CO₂/PDMS in which a broad distribution (characterized by a fractional exponential correlation function of the Williams-Watts type with α = 0.58) is observed, a sharp distribution with a fractional exponent, α, of 0.99 is found for the CO₂/PIB system. Instead of assuming an Arrhenius type temperature dependence, we used a Williams-Landel-Ferry type temperature dependence and found it to be better suited to describe the behavior of this system. PIB is a densely packed “strong” chain polymer which responds gradually to the temperature variation and gas sorption. In contrast PDMS is a relatively loosely packed “fragile” polymer with a propensity to exhibit rapid dynamic responses to the temperature change and gas sorption. © 1993 John Wiley & Sons, Inc.     

Molecular dynamics calculation to clarify the relationship between structure and mechanical properties of polymer crystals: the case of orthorhombic polyethylene

The molecular dynamics (MD) technique was used to calculate the temperature dependence of the structure, molecular motion, and mechanical property of the orthorhombic polyethylene (PE) crystal. The potential functional parameters reported by Karasawa et al. (J Phys Chem, 95 (1991) 2260) were refined further so that the vibrational frequencies of infrared and Raman bands, measured by us at ultra-low temperatures for the normal and fully deuterated PE, could be reproduced well. The flip-flop motion around the chain axis and the torsional motion of the skeletal chains were found to start above ca. 350 K and increase the amplitude of these motions progressively. Coupling these two types of chain motion resulted in a steep increase of the thermal vibration parameters or the mean-square-displacements of carbon and hydrogen atoms, corresponding well with the X-ray data. The lattice constants and the related linear thermal expansion coefficients were also found to be in good agreement with the observed data. The calculated Young's modulus along the chain axis decreased gradually with the increasing temperature: 330 GPa at 0 K to 280 GPa at room temperature. The latter was in good agreement with the value of 280–305 GPa evaluated from the Raman measurement of the longitudinal acoustic mode. Young's modulus was found to relate intimately with the chain contraction caused by the skeletal torsional motion. Only 0.3% contraction of the chain resulted in the reduction of the modulus by ca. 35%. A similar behavior was also seen in the trigonal polyoxymethylene and nylon 6 α forms.     

The purity of SnCl4 as monitored by 35Cl nuclear quadrupole resonance

The nuclear quadrupole resonance (NQR) spectroscopy was used to control the comparative purity of three SnCl₄ samples subjected to successive stages of deep purification. The results showed that at 77 K the samples were identical in purity degree due to the ‘freezing’ of impurities into a separate fraction not affecting the perfection of the SnCl₄ crystal lattice. The results of relaxation measurements suggest that paramagnetic impurity atoms (Fe and Cr) contained in the samples in small amounts might be embedded into the crystal lattice causing extremely long spin–spin relaxation time.     

Cl NQR study of lattice dynamic and magnetic property of a crystalline coordination polymer {CuCA(phz)(H2O)2}n

Copper(II) compounds {CuCA(phz)(H₂O)₂}_n (H₂CA = chloranilic acid, phz = phenazine) having a layer structure of -CuCA(H₂O)₂- polymer chains and phenazine were studied by ³⁵Cl nuclear quadrupole resonance (NQR). The single NQR line observed at 35.635 MHz at 261.5 K increased to 35.918 MHz at 4.2 K. The degree of reduction of electric field gradient due to lattice vibrations was similar to that of chloranilic acid crystal. Temperature dependence of spin-lattice relaxation time, T₁, of the ³⁵Cl NQR signal below 20 K, between 20 and 210 K, and above 210 K, was explained by (1) a decrease of effective electron-spin density caused by antiferromagnetic interaction, (2) a magnetic interaction between Cl nuclear-spin and electron-spins on paramagnetic Cu(II) ions, and (3) an increasing contribution from reorientation of ligand molecules, respectively. The electron spin-exchange parameter ∣J∣ between the neighboring Cu(II) electrons was estimated to be 0.33 cm⁻¹ from the T₁ value of the range 20−210 K. Comparing this value with that of J = −1.84 cm⁻¹ estimated from the magnetic susceptibility, it is suggested that the magnetic dipolar coupling with the electron spins on Cu(II) ions must be the principal mechanism for the ³⁵Cl NQR spin-lattice relaxation of {CuCA(phz)(H₂O)₂}_n but a delocalization of electron spin over the chloranilate ligand has to be taken into account.     

35Cl NQR and 1H NMR studies of [C(NH2)3]AuCl4, [C(NH2)3]2PtCl4, and [C(NH2)3]2PdCl4

The temperature dependence measurements of ³⁵Cl NQR frequencies and ¹H NMR spin-lattice relaxation time T₁ were carried out for guanidinium tetrachloro-aurate(III), -platinate(II), and -palladate(II). The gold(III) complex showed four NQR lines at various temperatures between 77 and 344 K, while the platinum-(II) and palladium(II) complexes gave two NQR lines in the temperature ranges 77–169 K and 77–220 K, respectively. An unusual phase transition was located at 363 K for the gold(III) complex. The high-temperature phase was easily supercooled. All the complexes studied yielded a T₁ minimum attributable to the reorientation of the planar cation about its C₃ axis. The motional parameters were evaluated. The Zeeman-quadrupole cross relaxation between protons and chlorine nuclei was observed for the platinum(II) and palladium(II) complexes at various temperatures below room temperature, while it was also detected for the high-temperature phase of the gold(III) complex.     

Low-frequency vibrational modes and temperature dependence of NQR frequencies in 1,2,4,5-tetrabromobenzene

A temperature variation study of the nuclear quadrupole resonance (NQR) frequencies for the two resonance lines in 1,2,4,5-tetrabromobenzene was carried out in the range 77–300 K. The far-infrared spectrum of 1,2,4,5-tetrabromobenzene was recorded and the low-frequency vibrational modes noted. From the nine observed frequencies, the torsional modes contributing to the change in NQR frequencies with temperature are identified by correlating the calculated values of the NQR frequencies at different temperatures with the observed values.     

57Fe-labeled octamethylferrocenium tetrafluoroborate. X-ray crystal structures of conformational isomers, hyperfine interactions, and spin-lattice relaxation by Moessbauer spectroscopy

X-ray structure determinations of two different single crystals of octamethylferrocenium tetrafluoroborate (OMFc(+)BF(4)(-)) revealed conformational polymorphism with ligand twist angles of 180 degrees and 108 degrees , respectively. Their concomitant occurrence could be explained by the small lattice energy difference of 3.2 kJ mol(-1). Temperature-dependent Moessbauer spectroscopy of (57)Fe-labeled OMFc(+)BF(4)(-) over the range 90 < T < 370 K did not show the anomalous sudden increase in the motion of the metal atom as observed in neutral OMFc. Broadened absorption curves characteristic of relaxation spectra were obtained with an isomer shift of 0.466(6) mm s(-1) at 90 K. The temperature dependence of the isomer shift corresponded to an effective vibrating mass of 79 +/- 10 Da and, in conjunction with the temperature dependence of the recoil-free fraction, to a Moessbauer lattice temperature of 89 K. The spin relaxation rate could be better described by an Orbach rather than a Raman process. At 400 K, a reversible solid-solid transition to a plastic crystalline mesophase was noted.