Excited state dynamics and energy transfer rates in Sr3Tb0.90Eu0.10(PO4)3

The emission spectrum of neat Sr₃Tb(PO₄)₃ upon excitation at 337 nm in the levels above ⁵D₃ is dominated by ⁵D₄ emission and no significant emission from ⁵D₃ is observed due to efficient cross relaxation involving the Tb³⁺ levels. On the other hand, the emission spectrum of the same host containing 10 mol% Eu³⁺ upon excitation at the same wavelength (in the Tb³⁺ levels) is dominated by strong emission bands from the ⁵D₀ level of Eu³⁺. This clearly indicates that Tb³⁺→Eu³⁺ energy transfer is present. The excitation spectrum of the Eu^{3+ 5}D₀ emission is dominated by Tb³⁺ bands extending in the UV region.The presence of 10 mol% Eu³⁺ in Sr₃Tb(PO₄)₃ very strongly shortens the ⁵D₄ decay time. The decay curve is not far from exponential, indicating that the energy transfer to Eu³⁺ is accompanied by fast energy migration. The transfer regimes are identified and the donor–donor and donor–acceptor transfer microparameters are quantified under the assumption of electric dipole–electric dipole interactions.     

Lattice and molecular dynamics in (ND4)2FeCl5· D2O

We have measured the thermal dependence of the f factor and the line shift of the title compound, to determine the (-2) and (+2) moments of the Fe frequency spectrum. The latter can be approximated by a superposition of an intramolecular and an intermolecular mode. Our determined frequencies are consistent with the spectroscopic data and previous results for NH₄ nondeuterated compound. This revised version was published online in August 2006 with corrections to the Cover Date.     

Observation of87Rb NMR satellite transitions in the commensurate and incommensurate phases of Rb2ZnCl4

It is shown that the first order quadrupole split NMR satellite transition frequencies of the⁸⁷Rb nucleus can be detected in the paraelectric, incommensurate and ferroelectric phases of Rb₂ZnCl₄. From rotation patterns the electric field gradient tensor at the Rb sites is determined for the paraelectric phase. The data demonstrate a considerable influence of the structural changes in the incommensurate and ferroelectric phases on the observed NMR transition frequencies. For some crystal orientations the satellite transitions are followed through the incommensurate into the ferroelectric phase. Whereas in the former typical quasi continuous spectra are observed in the latter several sharp lines appear. The results are discussed in relation to the structural changes at the phase transitions.     

Critical relaxation of short range correlations in the mixed crystal Rb1-x (ND4)x D2PO4

We have used thermal neutron scattering to investigate the possible dynamical origin of the short range correlations being typical for the glass phase of the mixed crystals Rb_1–x(ND₄)_xD₂PO₄. A quasielastic spectrum has been found for these correlations on top of a very broad spectrum associated with local correlations. The temperature dependence of these spectra together with their elastic components has been determined with an energy resolution of 0.14 meV. A common freezing temperature of about 100 K is observed below which the spatial correlations stop to increase and the scattering becomes elastic within the instrumental time scale.Dedicated to K. Dransfeld on the occasion of his 60th birthday     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

DFT - based study of electronic structures and mechanical properties of LiTaO3: ferroelectric and paraelectric phases

Abstract

By applying ab initio calculation within density functional theory (DFT), we study the structure parameters, electronic band structure, elastic coefficients, polycrystalline elastic properties, anisotropy factors and Debye temperature of ferroelectric and paraelectric phases of LiTaO₃ within the generalised gradient approximation at ambient pressure. The atomic structure in both phases is fully relaxed and the lattice constant, angle and atomic positions are well consistent with experimental values. The computed single-crystal elastic coefficients indicate that mechanical stability of LiTaO₃ in both phases is confirmed using the generalised Born criteria. The shear, bulk and Young’s modulus, Poisson’s ratio, and Vickers hardness were computed according to theoretical elastic constants by Voight–Reuss–Hill method. Several anisotropy factors and indexes are computed to illustrate mechanical anisotropy. Both phases are shown to be weakly anisotropic. The Debye temperature is estimated using the longitude and transverse elastic wave velocity of the ideal polycrystalline LiTaO₃ aggregates. We have found that LiTaO₃ in both phases has an indirect energy band gap. The differences in the electronic structure and density of states for both phases are quite small. Our results indicate that the mechanical and bonding properties of both phases are very similar. The obtained results were compared with the available experimental and theoretical values.     

1H NMR study of molecular dynamics and phase transition in (NH4)2ZnBr4

The proton second moment (M ₂) and spin-lattice relaxation time (T ₁) have been measured in (NH₄)₂ZnBr₄ in the range 77–300 K. The room-temperature spectrum shows a structure which disappears around 243 K. The signal is strong and narrow even at 77 K. Proton T ₁ shows a maximum at 263 K, caused by spin rotation interaction and decreases with decreasing temperature till 235 K, where it shows a sudden increase. Below 235 K, again it decreases and shows a slope change around 216.5 K (reported T_c ). From 216.5 K, T ₁ decreases continuously without exhibiting any minimum down to 77 K. The narrow line at 77 K, and absence of a T ₁ minimum down to 77 K indicate the possibility of quantum mechanical tunnelling in this system. Motional parameters such as activation energy and pre-exponential factor have been evaluated for the reorientational motion of the NH⁺ ₄ ion.     

The structure of the glass phase of Rb1−x(ND4)xD2PO4

X-ray scattering techniques have been used to study the diffuse scattering from a single crystal of Rb_1–x(ND₄)_xD₂PO₄ withx=0.65. This system has a structural glass phase at low temperatures resulting from the competing ferroelectric interactions of RbD₂PO₄ and antiferroelectric interactions of (ND₄)D₂PO₄. The diffuse scattering shows a broad peak with a maximum occurring at a wavevector of about 0.3a ^*, and the intensity of these peaks is surprisingly different for wavevectorsq on opposite sides of the Bragg reflections. A model of the D bonding is developed which suggests that the diffuse scattering arises from the interaction between ferroelectric displacements alongc, ferroelectric displacements alongb, and transverse acoustic modes polarized alongb andc. The model accounts for the incommensurate wavevector and, qualitatively, for the intensity of the diffuse scattering around different Bragg reflections. The temperature dependence of the scattering is also measured.     

Statics and dynamics of the modulation in incommensurate Rb2ZnBr4 as detected by NMR

The dynamics of the incommensurate modulation of Rb₂ZnBr₄ is investigated near the transition to the normal high-temperature phase using first-order quadrupole effects in nuclear magnetic resonance (NMR).⁸⁷Rb NMR spectra and two-dimensional⁸⁷Rb NMR exchange spectra are reported. All results can be described consistently in terms of a static modulation in the incommensurate phase without any indication for “floating” or large-scale fluctuations of the modulation wave. The spectra taken about 135 K below T_i in the lower incommensurate phase well above the soliton regime show no indication for the existence of a higher-order commensurate modulation in Rb₂ZnBr₄.