1H-ENDOR investigations on gamma-irradiated betaine calcium chloride dihydrate at room temperature

The ENDOR technique is applied to study the structure of the free radical N(CH₃)₃, found in the high temperature phase in the incommensurate crystal BCCD after γ-irradiation. The radical possesses a planar structure with strong deviation from the C₃ symmetry. The hybridization of the nitrogen atom is sp². Each of the three methyl groups exhibits a single ENDOR line, indicating the rotation of groups at room temperature. The deviation of the¹H hyperfine tensors of the methyl groups from axial symmetry is not a hint as to a hindered rotation of the groups. This is predicted by the C₂ symmetry of the system consisting of a π orbital and a rotating CH₃ group.     

Elastic neutron scattering and dielectric behaviour of 4% brominated betaine calcium chloride dihydrate (BCCD)

We report a combined experimental study by means of elastic neutron scattering and dielectric measurements of a partially deuterated and brominated BCCD (Betaine Calcium Chloride Dihydrate) crystal. The lowest-temperature phase is one-dimensional modulated and characterized by the coexistence of different commensurate domains (with = 1/4, 4/17, 2/9 and 1/5 on cooling), but with a clear predominance of the five-fold phase. A huge global thermal hysteresis of the wave-vector of the modulation, attaining values of about 9 K in the incommensurate phase and up to 15 K in the “harmless” low temperature part of the phase diagram, is observed up to . The role of lattice defects on this phenomenon is discussed. Similarly to the behaviour of the pure compound, the structural modulation evolves on cooling towards a soliton regime (growth of third and fifth-order satellite peaks), probably with respect to a non-stabilized non-modulated ferroelectric phase. The critical temperatures deduced from dielectric constant and pyroelectric current measurements are in very good agreement with those obtained from neutron scattering. The dielectric anomaly observed in at K, and known as the “-anomaly”, could not be related with any special feature detected in the neutron data, and in particular no correlation between this anomaly and the appearance of the soliton regime can be established. Received 26 October 1998     

1H one- and two-dimensional five-pulse ESEEM investigations on a radiation center in betaine phosphite single crystals

1D and 2D five-pulse ESEEM experiments on a PO ₃ ^2? center in γ-irradiated betaine phosphite are presented to study the protons bound to the radical in more detail. The ESEEM results are in accordance with previous ENDOR investigations. From the 2D fivepulse ESEEM experiments the¹H ENDOR assignment in the ferroelectric ordered state of betaine phosphite could be completed. Additionally, the occurrence of ordered proton states in the disordered paraelectric high-temperature phase and of disordered proton states in the ordered ferroelectric low-temperature phase as well could be observed due to the enhanced resolution of the 2D method.     

Magnetic resonance investigations of phase transitions and modulation wave motions in incommensurate solids

We measured⁸⁷Rb nuclear magnetic resonance (NMR) and³⁵Cl nuclear quadrupole resonance (NQR) Hahn spin-echo magnetization decays in the incommensurate (I) phase of Rb₂ZnCl₄ and, in each case, obtained a Hahn echo decay that was shorter than the Carr-Purcell-Meiboom-Gill decay and one which decayed with a time constant proportional to the cube of the echo time. From these measurements we obtained from both the⁸⁷Rb NMR and³⁵Cl NQR measurements values for the diffusion coefficients that are comparable in magnitude, a fact that strongly supports the existence of slow modulation wave diffusionlike motions in the I phase, since such motions should affect both Rb and Cl ions similarly. In addition, we used⁸⁷Rb two-dimensional exchange-difference NMR to study atomic motions in the incommensurate (I) and paraelectric (P) phases to elucidate the nature of the I-P transition. We measured as a function of the mixing time the frequency shifts of the cross peaks from the main diagonal and observed a gradual increase towards an asymptotic value in the I phase but a sudden jump to the final value in the P phase. We interpreted the motions observed in the P phase as normal modes arising from simultaneous reorientations of ZnCl₄ tetrahedra and corresponding Rb ions displacements between two sites. These normal modes freeze out in the I phase and change to the diffusionlike motion of the modulation wave. We also performed³⁵Cl NQR lineshape andT ₁ measurements in K₂ZnCl₄ and obtained conclusive evidence for the presence of a narrow 1q (singly modulated) I phase between 146 and 149 K.     

On the satellite extinction in incommensurate phase

For ZnP₂ and CdP₂ crystals in incommensurate phase selective superstructure X-ray reflections are observed. As shown a phason and amplitudon excitation modes do not result in this selective extinction of satellites. Apparently, it is associated with a modulation wave form in the incommensurate phase. The X-ray spectrum peculiarity of incommensurate crystals is discussed taking into consideration systematic and selective extinction of satellites.     

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.     

On the incommensurate phase in modulated Heisenberg chains

Using the density matrix renormalization group method (DMRG) we calculate the magnetization of frustrated S=1/2 Heisenberg chains for various modulation patterns of the nearest neighbour coupling: commensurate, incommensurate with sinusoidal modulation and incommensurate with solitonic modulation. We focus on the order of the phase transition from the commensurate dimerized phase (D) to the incommensurate phase (I). It is shown that the order of the phase transition depends sensitively on the model. For the solitonic model in particular, a k-dependent elastic energy modifies the order of the transition. Furthermore, we calculate gaps in the incommensurate phase in adiabatic approximation. Received: 9 March 1998 / Accepted: 17 April 1998     

Raman spectroscopic study of tris-sarcosine calcium chloride in the antiferroelectric phase

The polarized Raman spectra of (CH₃NHCH₂COOH)₃CaCl₂ (TSCC) have been obtained applying hydrostatic pressure in the paraelectric, ferroelectric and in the pressure-induced antiferroelectric phase. The phase transition between the paraelectric or the ferroelectric and the antiferroelectric phase appears to be of first order. No cell doubling could be observed in the antiferroelectric phase. The space group $\text{P2}{}_1\text{a (C}{}^5{}_{\mathrm{2h}}\text{)}$ for TSCC in this phase is compatible with our experimental results. The pressure-dependence of the Raman-active soft mode is discussed qualitatively.