Paramagnetic resonance in phosphorescent aromatic hydrocarbons

Electron resonance spectra have been recorded of the lowest triplet states of benzene, toluene, triptycene and tribenzotriptycene. The experiments were carried out by ultra-violet irradiation of these molecules in rigid glass solutions both at 77°k and 20°k. From an analysis of the line shape of the spectra, which prove to be strongly temperature dependent, the following conclusions could be drawn.

Benzene in its first triplet state has a configuration of lowest energy which is not a regular hexagon. This finding, supported by the results for toluene, was substantiated by SCF-MO calculations; it is in agreement with a recent analysis by Liehr and Moffitt. Tunnelling between equivalent conformations of benzene is thought to occur at a rate of the order of 10⁹–10¹⁰ sec^-1.

The spectra of the phosphorescent states of triptycene and tribenzotriptycene are dominated by intramolecular excitation transfer between the benzene or naphthalene sub-systems. In triptycene at 77°k transfer occurs at a rate ? 10¹⁰ sec^-1, so that one observes the resonance signal of a triplet exciton. In tribenzotriptycene the transfer is somewhat slower. The rate of excitation transfer decreases with temperature and at 20°k most of the excitation in tribenzotriptycene is effectively trapped in the naphthalene sub-systems.     

Paramagnetic resonance linewidth of EuO near the curie temperature

Measurements of the EPR linewidth ΔH of EuO at 9 GHz are reported in the temperature range of 66–300° K, with particular attention to the region near T_c (69.6° K). Comparison with the earlier data of Eastman at 25 GHz in the critical region shows considerable suppression of ΔH at 25 GHz. The temperature-dependent behavior of ΔH in EuO at 9 GHz is similar to the observations in CrBr₃ and it is in qualitative agreement with the zero-field predictions of Huber and Maleev. The quantitative discrepancies are believed to be due to the effect of the resonance magnetic field on EPR spin dynamics near T_c and an inadequate decoupling of the four-spin correlation functions used in the theories.     

Paramagnetic resonance of nickel doped ZnS and CdS crystals

EPR measurements were carried out on nickel doped ZnS and CdS crystals at 4.2°K and 9.3 Gc/sec. In ZnS crystals the isotropic line corresponding to the naturally occuring nickel isotopes ⁵⁸Ni and ⁶⁰Ni is significantly narrower than previously reported. The single line attributed to natural nickel has been observed in CdS crystals. The hyperfine structure has been studied on samples enriched in ⁶¹Ni. The angular dependence has been thoroughly investigated.     

Paramagnetic defects in ZnSe crystals doped with iron ions

The electron paramagnetic resonance (EPR) spectra of iron-doped ZnSe single crystals were studied. In addition to cubic Fe³⁺ and Mn²⁺ centers and also Fe²⁺, and Cr²⁺ centers, monoclinic Fe³+ complexes locally compensated by Cu+ ions were revealed. Some trigonal centers with a spin of 3/2 were also found and studied. The zero-field splittings of monoclinic centers were measured, and the parameters of the monoclinic and trigonal spin Hamiltonians were determined. The nature of trigonal centers was discussed.     

Paramagnetic oil emulsions as oral magnetic resonance imaging contrast agents

The combination of a paramagnetic agent with an oil emulsion can uniformly enhance the small bowel. We discovered that the entire small bowel becomes homogeneously brighter than its surroundings when imaged with all commonly utilized pulse sequences. We have tried various combinations of ferric ammonium citrate, ferrous sulfate, gadolinium-DPTA and corn oil, olive oil and peanut oil. All paramagnetic oil emulsions tested were uniformly distributed throughout the small bowel, but the enhancement effect is much stronger with the ferric ammonium citrate and gadolinium-DPTA oil emulsions. We have also developed a mixture of Geritol, corn oil, ice cream and milk, which uniformly coats the small bowel wall, has good enhancement effect, tastes good, and is nutritious. With this dietary contrast, retroperitoneal structures including the pancreas can be well delineated. We conclude that the combination of a paramagnetic agent with an oil emulsion can work as a safe and effective magnetic resonance imaging (MRI) oral contrast agent with high patient acceptance.     

Paramagnetic resonance study of fluctuations near phase transition in triglycine sulphate

The EPR line widths of the high and the low field resonances of Cr³⁺ in triglycine sulphate (TGS) show two distinct anomalous broadenings near T_c. One is associated with a change in the motional frequency of the hindered rotation of the NH₃ groups and the other is related to the fluctuation of the polarization. Just below T_c there is a two fold splitting of the resonances which has a$\text{(}\text{T}{}_{\mathrm{c}}\text{?}\text{T}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ temperature dependence indicating the local geometry about the Cr³⁺ ion is determined by mean field theory.     

Paramagnetic resonance study of the structural phase transition in sodium azide

The electron paramagnetic resonance (EPR) of Mn²⁺ impurities in sodium azide (NaN₃) single crystals has been measured between 178 K and 300 K in order to study the transition between the monoclinic low temperature α phase and the trigonal high temperature β phase of NaN₃. The analysis of the EPR spectra yields the parameters of the zero-field splitting (zfs) in the spin Hamilton operatorD(S _ξ ² ?1/3S(S+1))+E(S _ξ ² ?S _η ² ) associated with any of four different pair states of a Mn²⁺ ion and a cation vacancy. The obtained zfs, which is temperature dependent in α-NaN₃ and constant in β-NaN₃, is consistent with a continuous phase transition atT _c =292 K. Using a point charge model for the crystal potential the zfs parameters are related to the lattice structure in the vicinity of the Mn²⁺ ion. The zfs is not consistent with the temperature dependent atomic displacements in α-NaN₃ obtained previously from an X-ray diffraction study. The critical exponents of the zfs parameters, derived in the temperature range 1 K<T _c ?T<114 K, differ from the critical exponents of atomic displacements in α-NaN₃.     

Paramagnetic resonance of V in tetragonal GeO2

Anisotropic g and A tensors are found for V⁴⁺ in single crystal tetragonal GeO₂. The orbital mixing parameter λ, normalized radial average 〈1/r³〉/N and core polarization x/N are calculated, and λ is not anomalously low as reported from polycrystalline measurements.     

Paramagnetic resonance of Fe3+ ion in CdWO4 monocrystal

The paramagnetic spectrum of the Fe³⁺ ion in a CdWO₄ monocrystal was measured on a frequency of 9600 kMHz at 290°K. The spin-Hamiltonian of the Fe³⁺ ion was determined and had the form of (1). The constants derived for the spin-Hamiltonian areE/D=0·144±0·002,D=23·8 kMHz.

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Fe³⁺ CdWO₄

Fe³⁺ CdWO₄ 9600 kMHz 290°K. - Fe³⁺ (1), E/D 0,144±0,002 D 23,8 kMHz.

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In conclusion, the authors thank . Bárta and V. Kment from the Society for Chemical and Metallurgical Production in Ústí n/L for producing and supplying the monocrystals and for much valuable advice.     

Synthesis and investigation of iron fullerene clusters

Iron fullerene clusters are prepared by plasma chemical synthesis and investigated using electron magnetic resonance. It is shown that these clusters can be prepared both by plasma chemical synthesis of fullerenes with iron and by mixing of a fullerene solution with a powder of iron nanoparticles coated with carbon shells. A liquid chromatographic technique is proposed for separating iron fullerence clusters.     

Paramagnetic resonance evidence for phase transitions in bilayers of pure spin-labeled lipids

The paramagnetic resonance lineshapes for lipid bilayers composed of neat spin-labeled lipids have been studied as a function of temperature and structure of the lipid spin label. Evidence for phase transitions in the bilayers of two paramagnetic lipids is presented. Very stable hysteresis in the phase transition on heating and cooling of one of the lipids is observed and the effect of additives on the hysteresis is investigated. A plot of chemical potential versus temperature for lipid phases of different geometry is compatible with the observed hysteresis.     

Vacancy-solute complexes and their clusters in iron

In this contribution, several vacancy-solute complexes in iron are investigated theoretically from the viewpoint of positron annihilation. In particular, V-Si, V-P, V-Cr, V-Mn, V-Ni, V-Cu and V-Mo complexes are examined. In addition, nano-sized vacancy-Cu clusters in the Fe matrix are also studied. We concentrate on positron lifetimes and coincidence Doppler broadening profiles that bring complementary information about the studied complexes and their clusters. Positron calculations are carried out using the atomic superposition method employing realistic atomic configurations obtained recently using an ab initio pseudopotential method (vacancy-solute complexes) and Monte Carlo/molecular dynamics methods (vacancy-Cu clusters). The main aim of this study is to predict as to what extent such defects are detectable and differentiable using positron annihilation techniques. The results obtained are discussed in the context of experimental data available in the literature.     

Fission of doubly charged iron and aluminium clusters

We present a statistical fragmentation study of doubly charged iron and aluminum clusters of less than 60 atoms. At low excitation energies we find that the evaporation of one charged monomer is the most probable decay channel (asymmetric fission). When the excitation energy increases there is a competition between evaporation of a charged monomer and a charged dimer. For higher energies the number of channels increases and the multifragmentation mode appears at about 2.5 eV/atom. Presented by M.E. Madjet at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997.