On the deuteron magnetic resonance in single crystals of ND4Cl and ND4Br

The deuteron quadrupole coupling constants in ND₄Cl and ND₄Br have been measured. The results are 179.9±2.0 and 180.0±2.0 kHz, respectively. From the temperature dependence of the line width in ND₄Cl for the d. c. magnetic field along [100] the hindered rotation potential barrier of the ND₄ ⁺-ion was found to be 5.1 kcal/mole. In crystals containing moisture a narrow line component was observed, which is probably due to the formation of an eutectic solution.     

Transition energies of ND4Cl and ND4Br in the transition I⇄II

The energy of the transition I?II of ND₄Cl and ND₄Br was measured by using a direct differential calorimetric method. The results 1024 cal/mole for ND₄Cl and 847 cal/mole for ND₄Br were obtained. The accuracy was estimated to be about 2%. The approximate transition temperatures 169°C for ND₄Cl and 118°C for ND₄Br were observed.     

Neutron diffraction study of high-pressure-induced structural changes in the ammonium halogenides ND4Br and ND4Cl

Structural changes in the deuterated ammonium halogenides ND₄Br and ND₄Cl have been studied by neutron time-of-flight diffraction up to pressures of 45 and 35 kbar, respectively. Data on the equations of state and pressure dependence of the deuterium position parameter have been obtained. A comparison with the hydrogen-containing analogs showed that isotopic substitution of deuterium for hydrogen affects only slightly the compressibility of the systems under study, although the effect is noticeable for ND₄Cl. It has been established that the order-disorder transition from the phase with random deuterium distribution (CsCl cubic structure, space group Pm3m) to the ordered phase (same structure, space group ) occurs in both compounds at the same critical value of the position parameter u=0.153±0.002, which is apparently the same for all ammonium halogenides, and, possibly, for other systems of this structural type as well. Fiz. Tverd. Tela (St. Petersburg) 40, 142–146 (January 1998)     

Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)

Successive structural phase transitions of (4-ClC₆H₄NH₃)₂CuCl₄, which occur in a very narrow temperature range were reinvestigated by Fourier transform nuclear quadrupole resonance (FT NQR) measurements. The phase transitions at 275.5 and 277.0 K were confirmed. The effect of the deuteration of the ammonium end on these transitions was studied. The³⁵Cl NQR frequencies of organic cation were observed to decrease by about 4 kHz and the phase transition temperatures to decrease by about 2 K by the deuteration, suggesting that the ?NH₃ ⁺ … Cl hydrogen bond is weakened by the deuteration. The magnetic phase transition temperature of 8.6 K showed no remarkable change within experimental error by the deuteration. It was found that the magnetically ordered state is broken by the radio-frequency magnetic field of about 15–35 Oe usually employed in pulsed NQR. However, in the deuterated compound (4-ClC₆H₄ND₃)₂CuCl₄, the ordered state was found to be stabler for the usual radiofrequency power. By combining with the NQR data of (4-ClC₆H₄NH₃)₂CuBr₄ and (3,5-Cl₂C₆H₃NH₃)₂CuCl₄, the possibility is discussed of tuning the interlayer interaction between the organic cation layer and the inorganic complex anion layer by the halogen substitution in the organic cation as well as by the halogen replacement in the inorganic complex anion.     

Molecular Rydberg transitions: The lowest-energy Rydberg transitions of s-type in CH3X and CD3X,X = Cl,Br, and I

The absorption spectra associated with transitions to the lowest-energy s-type Rydberg states of CH₃X and CD₃X, X = Cl, Br, and I, have been measured and analyzed. The spectra of the bromides and iodides consist, individually, of four electronic origins of s-excitation type. The vibrational frequency of a given normal mode is more or less identical in all four excited states of any one molecule; and the excited state/ground state ratios of the frequencies of any given normal vibrational mode are essentially identical for all four molecules (i.e., for 16 states, four for each of two bromides and two iodides). The spectra of the chlorides are amenable to a number of different vibronic analyses, none of them unique; these analyses are discussed.     

NQR study of phase transitions in CH$\mathsf{_3}$HgX (X = Cl,Br, I)

The temperature dependence of halogen nuclear quadrupole resonance (NQR) in the series CH₃HgX (X = Cl, Br, I) is measured with special emphasis on the structural phase transitions at T _c = 162 K, 310 K, and 400 K, respectively. In the temperature dependences of NQR frequencies similarities are observed and discussed in relation with the structure and thermal vibrations on both sides of the phase transition. On the basis of known data a mechanism for the three analogous phase transitions is proposed. The chlorine spin-lattice relaxation behaviour in CH₃HgCl can be explained by a competition of fast thermal fluctuations of MMX molecules across the high temperature (h.t.) mirror plane and of infrequent transitions to the other equivalent fluctuation mode across the orthogonal h.t. mirror plane. Proton high temperature relaxation is probably dominated by the same slow motion, but at lower temperatures some other mechanism involving magnetic coupling prevails.Received: 23 June 2003, Published online: 15 October 2003PACS: 64.70.Kb Solid-solid transitions - 61.66.Fn Inorganic compounds - 76.60.Gv Quadrupole resonanceSupported in part by the Ministry of Education, Science and Sport, Republic of Slovenia     

Static,anharmonic and phonon properties of ND4I

A detailed investigation of the phonon dispersion and static and anharmonic properties has been carried out for ND₄I using an extended three-body force shell model (ETSM) developed by Singh and Chandra. The ETSM results for phonon dispersion show better agreement with the experimental data than those obtained from the deformation dipole and rigid shell models. Calculated values have also been obtained for some other properties.     

High-pressure magnetic and structural properties of TiOX (X=Cl,Br)

We report high-pressure diffraction and magnetization measurements to demonstrate that the partial collapse of electronic gap at high-pressure insulator to metal transition reported in TiOCl (C. Kuntscher et al. Phys. Rev. B 74 184402 (2006).) corresponds to a Ti³⁺–Ti³⁺ dimerization at room temperature within the space group P2₁/m. The shortest Ti–Ti distance is comparable to that of the Ti metal, but a Peierls-like distortion prevents a metallic behaviour.     

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.     

Proton and deuteron magnetic resonance of methanes,silanes and GeH3D dissolved in nematic liquid crystals

The proton and deuteron magnetic resonance spectra of CH₄, CH₃D, CH₂D₂, CHD₃, CD₄, SiH₄, SiH₃D, SiH₂D₂, SiH₃D, SiD₄, GeH₃D, dissolved in nematic liquid crystals, are reported. It was found that these molecules, which are essentially tetrahedral, exhibit anisotropic interactions and are partially oriented in the nematic phase. This effect is presumably due to slight deformations induced by the anisotropic medium. Some of the aspects related to the interpretation of the results are discussed.     

High-resolution 31P nuclear magnetic resonance study of phase transitions in TlH2PO4

High-resolution ³¹P nuclear magnetic resonance (NMR) techniques were employed to study a KH₂PO₄-type ferroelectric system, TlH₂PO₄. A marked temperature dependence of the isotropic chemical shift below the ferroelastic phase transition temperature is indicative of an electronic instability. The NMR linewidth showed a discontinuity at the ferroelastic phase transition, and the anisotropy was measured to increase rapidly below the antiferroelectric phase transition. Thus, the changes in the microscopic environments associated with the phase transitions were sensitively reflected in a characteristic manner.     

51V nuclear magnetic resonance in polycrystalline ferroelastic BiVO4

Nuclear magnetic resonance studies on polycrystalline ferroelastic BiVO₄ indicate that the ⁵¹V electric field gradient asymmetry parameter is an order parameter in the ferroelastic transition. Using ∩ = A(T?T_c)^B, B is found to be 0.48(5), in good agreement with earlier studies of this material. Near the phase transition above and below, the vanadium nuclear quadrupole coupling is constant with a value of 4.8(1) MHz.     

Electronic states and transitions of the TeX (X = C1, Br,I) radicals

Ab initio multireference configuration interaction calculations including spin-orbit coupling have been carried out for the first time for valence electronic states of the TeX (X = Cl, Br, I) radicals and compared with the results for the isovalent TeF and IO systems obtained earlier at a similar level of theoretical treatment. The calculated spectroscopic constants are in good agreement with experimental data in the rare cases when the latter are available. It is shown that the X² II(σ²π⁴π?³) ground state bonding becomes consistently weaker down the TeX group (calc. D_e, = 25480cm^?1 for TeF, 12 100cm^?1 for Tel) due to the more covalent character of bonding in the heavier radicals. The first excited state, A ⁴Σ^? (π?→ σ?), is calculated to be bound in all systems. It is split into Ω 1/2 and 3/2 components, with regular ordering in the Franck-Condon region, opposite to that of the ground X²II state. For larger internuclear distances, the A₁ ⁴Σ^? _1/2 state undergoes an avoided crossing with X₂ ²II_1/2, which causes a shoulder in the X₂ potential curve and also leads to a crossing between the A₁, and A₂ curves and large distinctions in their vibrational frequencies. The π? → σ? B²Σ^?, C²δ, and 1 ²Σ⁺ states are calculated to lie next in energy. They are all bound in the lightest of the TeX radicals, TeF, but successively lose their bonding character down the group. In contrast to oxygen monohalides, the 2²II(σ²π³ π?⁴) state has a repulsive potential curve. Electric dipole transition moments and radiative lifetimes have also been calculated for the low lying bound states in all systems. Most of them are found to be quite weak. The A^1,2 → X^1,2 spectra are dominated by parallel contributions, with the A₂ → X₁ being the strongest one. The T values for this transition are quite similar and lie in the 17–30 μs range. Radiative lifetime values for the B → X^1,2 transitions demonstrate very irregular behaviour for various, TeX radicals, due to strong admixture of A⁴Σ^? character to the X^1,2 states near the B²Σ^? potential minimum. The A^{1,2 4}Σ^? _1/2,3/2 and B²Σ^? _1/2 states of TeX (X = Cl, Br, I) still await their experimental observation.     

Total strength of the magnetic dipole resonance in 37Cl and 39K

The γ decay of resonance-like structures observed in the ³⁶S(pγ)³⁷Cl and ³⁸Ar(pγ)³⁹K reactions in the range of energies E _p = 0.8–2.8 MeV of accelerated protons has been studied. The M1 resonance on the ground and excited states of ³⁷Cl and ³⁹K nuclei has been identified. The position of the centroid and the total strength of the M1 resonance on the ground state of these nuclei have been determined and explained taking into account pairing forces.     

Cation mobility in the Cu6PS5X (X=Cl,Br, I) argyrodites

The electrical conductivity of Cu₆PS₅Cl shows purely Arrhenius behavior throughout the temperature range 170–450 K with no evidence of the 241 K thermodynamic phase transition previously reported. Cu₆PS₅Br exhibits two changes in activation energy. The first, at 251 K, apparently coincides with a previously determined thermodynamic transition. The second, at 321 K, is likely associated with a conduction transformation from ionic to electronic. The conductivity of Cu₆PS₅I is characterized by a cusp at a temperature of 194 K, far removed from a previously reported thermodynamic transition at 221 K. In addition, a broad and continuous change in activation energy appears to coincide with another previously reported phase transition at 270 K.     

The study of the vibrational spectra of NH4Cl and NH4Br at high pressures

The vibrational spectra of NH₄Cl at pressures of up to 2.6 GPa and of NH₄Br at pressures of up to 7 GPa are investigated by the method of inelastic incoherent scattering of neutrons. It is found that a linear baric dependence of a librational mode changes its slope above the pressure of transition from a disordered cubic phase into an ordered cubic phase with a CsCl-type structure. The slope of the baric dependence of the transverse optical translational mode remains invariant. Estimates for the Grüneisen parameters are presented and the shape of the potential function is calculated in the one-dimensional approximation for librational vibrations in disordered and ordered cubic phases with a CsCl-type structure. It is shown that the phenomena observed are attributed to the high anharmonicity in the disordered phase.     

14N and35Cl nuclear quadrupole double resonance study of the structural phase transitions in N-octylammoniumchloride

The structural phase transitions between the non-intercalated phases of the layer structure compound N-octylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the octylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.