Karel Kouřil

The dipolar endofullerene HF@C60

The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report the encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage with the escape of HF minimized. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large (1)H-(19)F J coupling typical of an isolated species. The dipole moment of HF@C60 was estimated from the temperature dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.

Dielectric, magnetic, and lattice dynamics properties of Y-type hexaferrite Ba0.5Sr1.5Zn2Fe12O22: Comparison of ceramics and single crystals

We prepared multiferroic Y-type hexaferrite Ba0.5Sr1.5Zn2Fe12O22 ceramics and compared their magnetic and dielectric properties with single crystal. Magnetic susceptibility and microwave resonance measurement revealed magnetic phase transition at TC=312 K, similar as in single crystal. Ferroelectric (FE) phase can be induced by external magnetic field in all investigated samples and the phase diagram in ceramics qualitatively resembles that of the single crystal. The range of magnetic fields, where the FE phase is induced, broadens after annealing of single crystal. Ceramics quenched after sintering exhibit several orders of magnitude lower conductivity than the single crystal. Heavily damped magnetic resonance was discovered in terahertz spectra at 10 K and its frequency softens below 5 GHz near TC. Number and symmetry of observed infrared (IR) and Raman active phonons correspond to paraelectric phase with D3d5 hexagonal structure. No evidence for a structural phase transition was found in the IR and Ram...

Bentonite/Iron Oxide Composites: Preparation and Characterization by Hyperfine Methods

Bentonite/iron oxide system is prepared by isothermal calcination of powder composed of bentonite clay and precursor containing ferric acetate. This preparation technique enables one to get the composite material directly, that is, iron oxide particles embedded in a bentonite matrix. Calcination temperature is varied from 320°C to 700°C. The resulting series of samples is characterized by local methods based on hyperfine interactions: 57Fe nuclear magnetic resonance (NMR) and the Mössbauer spectroscopy. The results show that the phase composition changes significantly in dependence on calcination temperature. The amount of maghemite phase rapidly increases up to °C and decreases abruptly for higher than 460°C.

Synthesis and Properties of Open Fullerenes Encapsulating Ammonia and Methane

Abstract We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH4 and NH3 are encapsulated, respectively. The 1H NMR resonance of endohedral NH3 is broadened by scalar coupling to the quadrupolar 14 n nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance 15N. The influence of the scalar relaxation mechanism on the linewidth of the 1H ammonia resonance is probed by variable temperature NMR. A rotational correlation time of τc=1.5 ps. is determined for endohedral NH3, and of τc=57±5 ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3@2 at 5 K identifies three vibrations of NH3 (ν 1, ν 3 and ν 4) redshifted in comparison with free NH3, and temperature dependence of the IR peak intensity indicates the presence of a large number of excited translational/ rotational states. Variable temperature 1H NMR spectra indicate that endohedral CH4 is also able to rotate freely at 223 K, on the NMR timescale. Inelastic neutron scattering (INS) spectra of CH4@1 show both rotational and translational modes of CH4. Energy of the first excited rotational state (J=1) of CH4@1 is significantly lower than that of free CH4.

Magnetically induced structural reorientation in magnetite studied by nuclear magnetic resonance

Phenomenon related to low symmetry phase of magnetite Fe3O4 below the Verwey transition is the switching of magnetic easy axis by external magnetic field connected with a structural transition. Results of nuclear magnetic resonance (NMR) studies of axis switching are presented, preceded by careful characterization by magnetic measurements. We detect changes in the F57e NMR spectra that evidence the structural transition interrelated with the axis switching. We also observe the switching process in time and analyze the dynamics of the phenomenon. Phenomenological approach according to Kolmogorov–Johnson–Mehl–Avrami is employed to find a link between the experimental data from magnetization measurements and NMR, showing that the effect observed by these two methods has the same origin. Additionally, NMR identifies separately the unswitched and switched phase during the switching process.

Electric field gradient in FeTiO3 by nuclear magnetic resonance and ab initio calculations

Temperature dependence of nuclear magnetic resonance (NMR) spectra of (47)Ti and (49)Ti in polycrystalline ilmenite FeTiO(3) was measured in the range from 5 to 300 K under an external magnetic field of 9.401 T. NMR spectra collected between 300 and 77 K exhibit a resolved quadrupole splitting. The electric field gradient (EFG) tensor was evaluated for Ti nuclei and the ratio of (47)Ti and (49)Ti nuclear quadrupole moments was refined during the fitting procedure. Below 77 K, the fine structure of quadrupole splitting disappears due to the enormous increase of anisotropy. As a counterpart, ab initio calculations were performed using full potential augmented plane waves + local orbitals. The calculated EFG tensors for Ti and Fe were compared to the experimental ones evaluated from NMR and the Mössbauer spectroscopy experiments.

Alignment of 17O-enriched water–endofullerene H2O@C60 in a liquid crystal matrix

We present a 17O and 1H NMR study of molecular endofullerene H2O@C60 dissolved in the nematic liquid crystal N-(4-methoxybenzylidene)-4-butylaniline (MBBA). The 17O NMR peak is split into five components by the 17O residual quadrupolar coupling, each of which is split into a triplet by the 1H-17O residual dipolar coupling and scalar coupling. The splittings are analysed in terms of the partial alignment of the encapsulated water molecules. Order parameters describing the alignment are estimated. It is found that the preferential orientation of the endohedral water molecule has the molecular plane perpendicular to the liquid crystal director.