The Muon F-µ+-F Hydrogen Bond-like Complex.

Muon spin rotation (µSR) and relaxation has been used to study the local magnetic structure of K3Fe5F15. A collinear F-µ+-F "hydrogen bond-like" symmetric double minimum type complex with a F...F distance of 2.8 Å and a separation between the two minima of 0.8 Å has been found in the paramagnetic phase. The apparent central position of the muon seems to be the result of fast muon tunneling between two equivalent minima in the F-µ+-F bond.

14N nuclear quadrupole resonance of some sulfa drugs.

The 14N nuclear quadrupole double resonance spectra of different polymorphs of sulfanilamide, sulfadiazine, sulfamerazine and sulfamethazine have been measured and the 14N quadrupole coupling tensors have been determined. The obtained 14N spectra are compared with those of other sulfa drugs like sulfathiazole. It is shown that different polymorphs can be easily discriminated. The application of this technique for non-destructive analysis, polymorph determination and quality control in the production of pharmaceuticals is stressed.

Resolving the quantum criticality paradox in O-18 isotopic SrTiO(3).

Recently there has been considerable interest in the displacive ferroelectric phase transition near T = 28 K in O-18 isotopic strontium titanate. Special efforts have been made to combine the quantum criticality exponents α = -2 (2D) or -3 (3D), δ = 3, and γ = 2 with the thermodynamic inequalities of Rushbrooke, Griffiths, Widom et al, which become exact equalities under the hypothesis of scaling. In particular, these have led others to the inference that γ = 2.0 and ß = 1.2 in SrTiO(3). First we show that this is mathematically incorrect and explain why (quantum criticality is exact only at T = 0, whereas the thermodynamic (in)equalities are valid everywhere except T = 0). Second, we show that the inferred values strongly violate a new equality, γ-2ß = ν(4-d-2η)>0, we derive from hyperscaling. Third, we show that the existing soft mode frequency data ω(T) from Takesada et al (2006 Phys. Rev. Lett. at press) yield above T(c) (from the Lyddane-Sachs-Teller relationship) γ = 1.0. Fourth, we remeasure ß from the polarization P(T) and find ß = 0.50 ± 0.02. Fifth, we remeasure the electric susceptibility and find that it perfectly satisfies the Salje-Wruck-Thomas equation, which requires γ = 1.0. The important conclusions are: (a) O-18 SrTiO(3) near T(c) is mean-field; (b) the thermodynamic scaling equalities of Rushbrooke, Griffiths et al are mathematically incompatible with quantum criticality theory; (c) a new hyperscaling relationship makes ß = 1.2 and ß>γ/2 impossible.

Calorimetric and dielectric studies of ferroelectric sodium nitrite confined in a nanoscale porous glass matrix.

Heat-capacity measurements of the sodium nitrite confined in a nanoscale porous glass matrix show that the intermediate incommensurate phase, present in the bulk, has disappeared and that the first-order ferroelectric transition becomes suppressed and gradual. The ferroelectric transition temperature is shifted considerably to lower temperatures. Two noncritical dielectric modes were observed; however, the observed giant growth of the dielectric constant on heating through the transition temperature TC is shown to be mainly due to the electrode polarization effect.

Order-disorder component in the phase transition mechanism of 18O enriched strontium titanate.

Ti and Sr nuclear magnetic resonance spectra of 18O enriched SrTiO3 (STO-18) provide direct evidence for Ti disorder already in the cubic phase and show that the ferroelectric transition at T(C)=24 K occurs in two steps. Below 70 K rhombohedral polar clusters are formed in the tetragonal matrix. These clusters subsequently grow in concentration, freeze out, and percolate, leading to an inhomogeneous ferroelectric state below T(C). This shows that the elusive ferroelectric transition in STO-18 is indeed connected with local symmetry lowering and implies the existence of an order-disorder component in addition to the displacive soft mode one. Rhombohedral clusters, Ti disorder, and a two-component state are found in the so-called quantum paraelectric state of STO-16 as well. The concentration of the rhombohedral clusters is, however, not high enough to allow for percolation.

Unusual dynamic behavior in the isotropic phase of banana mesogens detected by 2H NMR line width and T2 measurements.

In this work the first experimental observation of a peculiar behavior in the isotropic phase of liquid crystals by means of 2H NMR is reported. In particular, two five-ring banana-shaped mesogens, the 1,3-phenylenebis{4,4'-(11-undecenyloxy)benzoyloxy}benzoate (Pbis11BB) and its 4-chloro homologue (ClPbis11BB), selectively deuterium labeled on their central rings, are the subject of our investigation. The dynamic behavior of the two liquid crystals was studied in their isotropic phases and in the nematic phase of ClPbis11BB by means of 2H NMR line width and spin-spin relaxation time (T2) analysis. The results obtained reveal that the unusual line broadening observed in the 2H NMR spectra in the isotropic phase, even far above the isotropic phase-mesophase transition, has a homogeneous nature, thus indicating the presence of reorientational motions much slower than in conventional isotropic liquid-crystalline phases.

Field cooled and zero field cooled 207Pb NMR and the local structure of relaxor PbMg1/3Nb2/3O3.

An isotropic 207Pb NMR spectrum corresponding to the glassy matrix with spherical shell type Pb shifts from the cubic sites, as well as an anisotropic spectral component corresponding to polar nanoclusters with a Pb shift parallel to the [111] direction, have been observed in a PbMg(1/3)Nb(2/3)O3 (PMN) single crystal. This represents a microscopic confirmation of the model of relaxors first proposed by Burns and Dacol. A sudden increase in the intensity of the anisotropic cluster line is seen for electric fields larger than the critical field around 210 K. This demonstrates the occurrence of an orientational percolation type transition to the field-induced ferroelectric phase with about 50% of the Pb nuclei still remaining in the spherical glass matrix. A similar though smaller increase of the intensity of this line is also seen in the zero field cooled data, demonstrating that relaxor PMN is an incipient ferroelectric.

NMR evidence for the coexistence of order-disorder and displacive components in barium titanate.

A quadrupole coupling induced 47Ti and 49Ti satellite background which transforms into well-defined satellite lines below T(c) in the ferroelectric phase has been observed in the cubic phase of an ultrapure BaTiO3 single crystal. The results demonstrate the coexistence of a displacive and order-disorder component in the phase transition mechanism and tetragonal breaking of the cubic symmetry due to biased Ti motion between off-center sites in the paraelectric phase above T(c).

Slater ice rules and H-bond dynamics in KDP-type systems.

We report on the first observation of the dynamics of correlated hydrogen switching among the six Slater D2PO4 configurations, induced by unpaired D3PO4 and DPO4 Takagi group diffusion in a deuteron glass Rb0.5(ND4)0.5D2PO4. The results obtained by two-dimensional (2D) 31P exchange NMR prove the validity of the Slater-Takagi ice rules and allow for the direct determination of the correlation time for the unpaired Takagi group visits to a given D2PO4 group.

Behavior of mesogenic molecules deposited at the alumina-air interface: a deuteron NMR study.

Thin molecular depositions of 4(')-pentyl-4-cyonobiphenyl (5CB) mesogenic molecules are investigated via quadrupole-perturbed deuteron nuclear magnetic resonance (DNMR) spectroscopy. Uniform and controlled thickness molecular surface depositions are prepared on the inner cylindrical surfaces of Anopore membranes by the solvent-evaporation technique. As a result, 5CB molecules are found in two different configurations: a bulklike one with parallel axial arrangement, and a surface one with planar radial arrangement. If the 5CB surface coverage exceeds c approximately 0.35, only the bulk state is present. In the coverage range between 0.015 and 0.35, the bulklike state and the surface layer coexist, conforming to a typical dewetting scenario. Below c approximately 0.015, only the surface layer is present. The dilution of the surface deposition with decreasing coverage is manifested as an increase in the DNMR doublet frequency splitting. The surface orientational order parameter Q, the surface biaxiality eta, and the diffusion coefficient D(S) are determined from the DNMR spectral patterns obtained at different sample orientations in the external magnetic field. These angular patterns prove that in highly diluted surface depositions the molecules lie flat on the surface. However, they are not frozen and their molecular axes rapidly reorient on the DNMR measurement time scale, typically 10(-4) s, while remaining confined to the surface. Simultaneously, molecules diffuse over the surface with a surface diffusion constant on the order of 10(-11) m(2) s(-1). Such molecular diffusion is responsible for an effective biaxiality on the DNMR time scale. However, an inherent biaxiality cannot be completely ruled out and thus may play a minor role. The surface phase has a two-dimensional (2D) gas character with some (possible) indicators of 2D-liquid properties.

Beltlike C(60)(-) electron spin density distribution in the organic ferromagnet TDAE-C(60).

The observed huge increase in the width of the (3C)NMR spectra of TDAE-C(0 )n the middle of the ferromagnetic phase at 10 K is due to a Jahn-Teller distortion of the C(60 )(-) which becomes visible in view of the resulting changes in the Fermi contact electron-(13)C NMR shifts. The shape of the (13)C spectra allows for a direct determination of the belt-like redistribution of the unpaired electron spin density on the C(60)(-) ions, which is responsible for the relatively high ferromagnetic transition temperature in this purely organic system.