Modernization of the x-band epr spectrometer bruker elexsys e580 for dynamic nuclear polarization

To study the effects of dynamic nuclear polarization (DNP) in the X-band (microwave frequency of 9 GHz), using the capabilities provided by commercial EPR equipment, a part of the EPR spectrometer associated with the excitation and detection of double electron-nuclear resonance signals (ENDOR) has been modernized. Using the developed preamplifier of NMR signals, a homemade “Kazan Nova II”NMR spectrometer was implemented into the radio frequency path of the EPR spectrometer. The tuning and matching circuits made it possible to observe the NMR and DNP signals on protons in the frequency range 14.5–15.2 MHz. The performance of the DNP equipment was tested for a solution of the stable nitroxyl radical TEMPOL in benzene and a crude oil sample. The DNP effects caused by the Overhauser and solid effects were observed. The modernization of the existing EPR equipment creates a basis for further expanding its capabilities to study DNP effects in various systems at different conditions (in the pulsed mode of saturation of the EPR lines, with the temperature lowering, under the action of optical excitation, etc)

Using DFT to calculate the parameters of the crystal field in Mn²⁺ doped hydroxyapatite crystals

Crystal field parameters for two nonequivalent positions Ca (I) and Ca (II) for hydroxy-apatite (HAp) crystals from the density functional theory (DFT) are calculated. Calculations are compared with the experimental electron paramagnetic resonance (EPR) spectra (registered at two microwave frequencies) for the synthesized Mn-HAp powders Ca9.995Mn0.005(PO4)6(OH)2. It is found that in the investigated species, the manganese is redistributed between both calcium sites with prevalence in Ca (I). Agreement between the calculated and experimental data proves that crystal field parameters in HAp can be calculated in the classical DFT model using the distributed electron density

Size-dependent concentration of N⁰ paramagnetic centres in HPHT nanodiamonds

Size-calibrated commercial nanodiamonds synthesized by high-pressure high-temperature (HPHT) technique were studied by high-frequency W- and conventional X-band electron paramagnetic resonance (EPR) spectroscopy. The numbers of spins in the studied samples were estimated. The core-shell model of the HPHT nanodiamonds was proposed to explain the observed dependence of the concentration of the N0 paramagnetic centers. Two other observed paramagnetic centers are attributed to the two types of structures in the nanodiamond shell

Probing Wave Functions of Electrically Active Shallow Level Defects by Means of High-Frequency Pulsed ENDOR in Wide Bandgap Materials: SiC, AlN, ZnO, and AgCl

In the high-frequency ENDOR experiments, the hyperfine (HF) interaction between the unpaired electron of the shallow donor or shallow acceptor and the nuclear spins of the Coulombic center and the surrounding atoms is determined, which is then translated into the spin density of the electronic wave function at the various atomic positions. The results of studying the spatial distribution of wave functions for shallow donors in ZnO, AgCl, AlN, and SiC crystals, ZnO-based nanostructures, and shallow boron acceptors in SiC will be presented. The change of the electronic wave function of a shallow donor in ZnO quantum dots (QDs) when entering the regime of quantum confinement by using the nuclear as probes has been observed. The model, based on the effective mass approximation (EMA), that describes a 1s-like wave function with the Bohr radius of ~ 1.5 nm for distant shells was tested. The EMA does not yield an appropriate description of the electronic wave function when the radius of the QD is reduced below the Bohr radius. The direct reconstruction of the wave function of the intrinsic shallow electronic center (SEC) and self-trapped excitons in AgCl was presented. The SEC was suggested to be an electron that is shallowly trapped by two adjacent silver ions on a single cationic site (split-interstitial position), so-called “latent image” in silver halides. The shallowly trapped electron of the STE is shown to behave like a hydrogen 1s electron, centered on the Ag+ lattice position, with a Bohr radius r0 = 1.51 nm that is in agreement with Bohr radius of SEC (r0 = 1.66 nm). For SEC in AgBr, r0 = 2.48 nm. It was demonstrated that dynamic nuclear polarization of nuclear spins due to hyperfine interactions with ligand nuclei can be achieved in ZnO (and based QDs) and AgCl by saturating the high-frequency EPR transition of a shallow donor at low temperatures corresponding to a high Boltzmann factor. Several types of shallow donors were indicated in AlN crystals: (i) affected by the DX-relaxation and (ii) with normal behavior. The strong HF interaction for light-induced SD in AlN support the assignment to the impurity in anionic sublattice (e.g. oxygen in N position). At the same time, a shallow donor with normal behavior can belong to Si or C in the Al position. The electronic structure of shallow donors and shallow acceptors in silicon carbide was investigated by the ENDOR method. The spin density of the N donor corresponding to the observed ENDOR lines was established to be p like in character and located mainly on the Si atoms for the k site in 4H-SiC, whereas for the three sites in 6H-SiC the spin density is s-like in character and located mainly on the C atoms. An explanation for the difference in the electronic wave function of the N donor in 4H-SiC and 6H-SiC can be found in the large difference in the band structure of the two polytypes and in the position of the minima in the Brillouin Zone. The electronic density for shallow B acceptor substituting Si in the k position is distributed in an ellipsoidal shape with the main symmetry axis making an angle of 70° with the c axis, i.e., along the direction of the B–C with main spin density

EPR of Radiation-Induced Nitrogen Centers in Hydroxyapatite: New Approaches to the Study of Electron-Nuclear Interactions

© 2020, Pleiades Publishing, Ltd. Abstract: Radiation-induced impurity nitrogen centers (NO32-) in nanosized powders of synthetic hydroxyapatite are studied by pulse EPR and pulse double-frequency EPR, which is named the NMR detected by electron–electron double resonance (ELDOR detected NMR, EDNMR) method. The EPR signals caused by the interaction of the electron of (NO32-) with the environmental nuclei (1H, 14N, and 31P) are identified, and the parameters of the hyperfine and quadrupole interactions of the electron with the 14N nuclei are determined. The possibility of using the EDNMR method in the X-band of microwave frequencies (νmw ≈ 9 GHz) at room temperature to obtain a detailed information about peculiarities of electron-nuclear interactions in hydroxyapatite is demonstrated

Plasma-Sprayed Manganese-Containing Tricalcium Phosphate Coatings on Titanium

Abstract—: Manganese-substituted tricalcium phosphates (TCPs), Ca3(PO4)2, containing 0–1.49 wt % manganese have been prepared by heterophase synthesis using mechanical activation. The percentage of manganese has been determined by inductively coupled plasma atomic emission spectroscopy and atomic absorption spectroscopy. The compounds have been characterized by X-ray diffraction, IR spectroscopy, EPR spectroscopy, and scanning electron microscopy (SEM). Ceramic coatings have been produced using an arc plasma source. The coatings have been characterized by X-ray diffraction and SEM with the use of energy dispersive X-ray analysis. They have been shown to consist of α-TCP and hydroxyapatite (Ca10(PO4)6(OH)2). Manganese ions have been shown to be incorporated into the crystal lattice of TCP. After holding in physiological solution at pH 7.4 for 90 days, neither manganese nor phosphorus was detected in the coatings. After holding in physiological solution, the coatings consisted of calcium carbonate, as was demonstrated by energy dispersive X-ray analysis. The coatings produced on titanium implants are promising for use in orthopedics and dentistry

Application of pulsed and high-frequency electron paramagnetic resonance techniques to study petroleum disperse systems

© 2020 The Authors. The spectral and relaxation characteristics of “free” organic radicals (FR) and vanadyl-porphyrin (VP) complexes in various petroleum disperse systems (PDS) like bitumen, petroleum, their high-molecular components and solutions were studied using stationary (conventional) and pulsed electron paramagnetic resonance (EPR) techniques in two frequency ranges (X-and W-bands, with the microwave radiation frequencies of about 9 GHz and 95 GHz, respectively). The features of the pulsed approaches (electron spin echo, modulation of the electron spin echo signal decay, electronic relaxation times) and high-frequency EPR for PDS investigations were examined. W-band EPR allows to resolve spectrally the lines from the different paramagnetic centers and more accurately determine their spectral characteristics. It is shown that the electron spin echo can be observed at room temperatures even at high magnetic fields of 3.4 T demonstrating the potential of application of pulsed EPR techniques for the low-cost oilfield measurements. Analysis of the VP transverse magnetization decay curve permits to identify electron-nuclear interactions with the14N and1H nuclei in situ while in the EPR spectra these hyperfine interactions usually cannot be detected. It is found from the W-band EPR measurements that FR lineshape cannot be fitted with isotropic parameters in contrast to the established X-band results. The observed effect of increasing the rates of electronic transverse relaxation in asphaltenes is described in the framework of a model of spectral diffusion between the fast-and slow-relaxing paramagnetic centers in supramolecular complexes of asphaltenes

ENDOR study of nitrogen hyperfine and quadrupole tensors in vanadyl porphyrins of heavy crude oil

We report the observation of pulsed electron-nuclear double resonance (ENDOR) spectrum caused by interactions of the nitrogen nuclei 14N with the unpaired electron of the paramagnetic vanadyl complexes VO2+ of vanadyl porphyrins in natural crude oil. We provide detailed experimental and theoretical characterization of the nitrogen hyperfine and quadrupole tensors

Coherent control of electron-nuclear states of rare-earth ions in crystals using radio-frequency and microwave radiation

We have demonstrated electron-electron and electron-nuclear spin manipulations of Gd3+ ion in CaWO4 crystal. The results suggest that the studied system is perspective for multiqubit implementation in quantum computing.Comment: 2 Pages, 5 Figure