Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Magnetic properties of MnO nanocrystals dispersed in a silica matrix

Magnetic nanocrystalline MnO particles have been synthesized in a silica glass matrix by the sol-gel method at calcination temperatures up to 1000 °C. EPR spectra of 0.1 mol% MnO doped silica gel and glasses studied in the temperature range 10-290 K show with the exception of those samples calcined at 900 and 1000 °C 6-line characteristic Mn(II) hyperfine (HF) lines. Additionally five spin-forbidden doublets have been observed at 100 K and below. Small spreads in spin Hamiltonian parameters (D and E) imply that the ligand field environments of Mn(II) ions embedded in the silica glass are nearly uniform. Monotonous decrease in HF linewidth in going from 120 °C gel to 800 °C calcined glass has been interpreted as the continuous decrease in population of isolated Mn²⁺ ions in silica glass matrix resulting in the decrease of magnetic dipolar interactions leading to the observed decrease in HF linewidth. XRD and TEM of sample calcined at 1000 °C shows the presence of nanocrystals of MnO having orthorhombic crystalline phase and sizes about 10 nm. The thermal behavior of magnetization (zero-field-cooled and field-cooled) and magnetic hysteresis of MnO nanocrystals in the 5-300 K temperature interval have demonstrated that the MnO nanocrystals display superparamagnetic-ferromagnetic transition at low temperatures. X-band EPR linewidth data plotted versus inverse of temperature (1/T) for samples calcined at 900 and 1000 °C (EPR recorded in the vicinity of 0.35 T applied field) depict similar transitions.     

Zn1−xMnxO : A typical member of the II-VI:Mn DMS family

ZnO:Mn thin films are grown by MOCVD technique. Mn(x) varies in 0<x<0.44 range. Vegrad’s law has been verified for the lattice parameters. EPR measurements prove the substitution incorporation of Mn²⁺ on zinc sites. The behavior of EPR line-width regarding temperature is discussed. All ZnO:Mn layers show antiferromagnetic interaction and a effective exchange constant. Observation of excitons, giant Zeeman effect, and trace of the Brillouin function is evidence for high quality of the crystal lattice and of substitutional incorporation of manganese ions in place of Zn, as Mn²⁺.     

Synthesis, crystal structure, Cu doped EPR and voltammetric studies of bis[N-(2-hydroxyethyl)ethylenediamine]zinc(II) squarate monohydrate

Crystal structure of [Zn(hydet-en)₂]·C₄O₄·H₂O (ZHES) (hydet-en is N-(2-hydroxyethyl)ethylenediamine) complex has been synthesized and characterized by analytical, spectroscopic (IR, UV/Vis) and voltammetric techniques. After doping Cu²⁺ ion, its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystalizes in monoclinic system with space group P2₁/c and with Z=4. Each hydet-en ligand acts as a tridentate ligand through the two N atoms and the hydroxyl O atom, resulting in a six coordinate Zn(II) ion. The EPR spectra were recorded in three perpendicular planes of Cu²⁺ doped ZHES single crystal. The calculated g and A values indicated that the paramagnetic center is rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The molecular orbital bond coefficients of the Cu(II) ion in d⁹ state is also calculated by using EPR and optical absorption parameters. The dianion SQ²⁻ is oxidized reversibly in two consecutive steps to the corresponding radical monoanion and neutral form.     

Diffusive EPR line width behaviour in two-dimensional Cu(Hippurate)2 4H2O single crystal

X-band EPR measurements were performed at room temperature on layered Cu(Hippurate)₂4H₂O single crystals. Despite the dimeric molecular structure the EPR spectra are characteristic for individual Cu-complexes with square-pyramidal structure and g-factors: g_x=2.045, g_y=2.085 and g_z=2.346. The anticipated zero-field splitting from dimers with S=1 is averaged out by interdimer exchange coupling within the layers. The dimers in adjacent layers are not exchange coupled as we determined from the two-component EPR spectra. Thus, the crystal is an ideal 2D magnetic system and shows a strong spin diffusion effect in the EPR line width. The spin diffusion contribution to the line width is described as P(3cos²Θ−1)² with which is much higher compared to other 2D copper(II) crystals. The background line width is due to dipolar coupling and non-resolved hyperfine structure. Exchange coupling was determined from the exchange narrowing effect as of about 0.1 cm⁻¹.     

Antiferromagnetic resonance studies in molecular magnetic materials

EPR spectroscopy has become an increasingly powerful tool to examine the spin states and dynamics of single-molecule magnets, but has not been exploited to probe bulk magnetically ordered phases of molecular magnets. In this article, we review the EPR spectra of antiferromagnets and canted antiferromagnets below T_N with particular reference to our own studies on the canted antiferromagnet, p-NCC₆F₄CNSSN (T_N=36 K). The antiferromagnetic resonance experiment allows the saturation of the sublattice magnetisation to be probed. In addition, the exchange and anisotropy fields (H_e and H_a), the spin-flop field (H_sf) and for canted antiferromagnets, the Dzyaloshinskii-Moriya field (H_DM), which gives rise to the spontaneous moment, can be determined.     

Non-equilibrium effects in copper vapor laser pumped Nd3+ doped PVA film: Photo-electon paramagnetic resonance and photoacoustic spectral investigations

Photo-EPR measurements carried out on Nd³⁺ -doped polyvinyl alcohol (PVA) films have shown that nearly 100% reduction occurs in the intensity of EPR of Nd³⁺ under in situ copper vapor laser (CVL) illumination (510.5 nm and 578.2 nm). The kinetics of decay and recovery were investigated. Photoacoustic (PA) spectra, observed under CVL pump condition had shown that the CVL induced changes were not due to photoinduced valence change, and that the CVL pumping creates highly favorable conditions for non-equilibrium population distribution in the excited electronic states. The complete disappearance of EPR under CVL pumping is attributed either to the possible equalization of population of |+〈 and |−〈 Zeeman components, through the decay of many excited states in the presence of magnetic field or configurational changes around Nd³⁺ shifting the resonance frequency. The former appears less probable in view of the relatively slower recovery of EPR signal.     

Double resonance experiments in low magnetic field: Dynamic polarization of protons by N and measurement of low NQR frequencies

The possibilities of dynamically polarizing proton spin system via the quadrupole ¹⁴N spin system in low magnetic field are analyzed. The increase of the proton magnetization is calculated. The polarization rate of the proton spin system is related to the transition probabilities per unit time between the ¹⁴N quadrupole energy levels and proton energy levels. The experiments performed in 1,3,5-triazine confirm the results of the theoretical analysis. A new double resonance technique is proposed for the measurement of nuclear quadrupole resonance frequencies ν_Q of the order of 100 kHz and lower. The technique is based on magnetic field cycling between a high and a low static magnetic field and observation of the proton NMR signal in the high magnetic field. In the low magnetic field the quadrupole nuclei and protons resonantly interact at the proton Larmor frequency ν_H = ν_Q/2. The quadrupole nuclei are simultaneously excited by a resonant rf magnetic field oriented along the direction of the low static magnetic field. The experimental procedure is described and the sensitivity of the new technique is estimated. Some examples of the measurement of low ¹⁴N and ²H nuclear quadrupole resonance frequencies are presented.     

Magnetic properties and EPR spectra of [Cu(L-arginine)2](NO3)2·3H2O

Magnetic and EPR data have been collected for complex [Cu(L-Arg)₂](NO₃)₂·3H₂O (Arg=arginine). Magnetic susceptibility χ in the temperature range 2-160 K, and a magnetization isotherm at T=2.29(1) K with magnetic fields between 0 and 9 T were measured. The observed variation of χT with T indicates predominant antiferromagnetic interactions between Cu(II) ions coupled in 1D chains along the b axis. Fitting a molecular field model to the susceptibility data allows to evaluate g=2.10(1) for the average g-factor and J=−0.42(6) cm⁻¹ for the nearest neighbor exchange coupling (defined as H_ex=-∑J_ijS_i·S_j). This coupling is assigned to syn-anti equatorial-apical carboxylate bridges connecting Cu(II) ion neighbors at 5.682 Å, with a total bond length of 6.989 Å and is consistent with the magnetization isotherm results. It is discussed and compared with couplings observed in other compounds with similar exchange bridges. EPR spectra at 9.77 were obtained in powder samples and at 9.77 and at 34.1 GHz in the three orthogonal planes of single crystals. At both microwave frequencies, and for all magnetic field orientations a single signal arising from the collapse due to exchange interaction of resonances corresponding to two rotated Cu(II) sites is observed. From the EPR results the molecular g-tensors corresponding to the two copper sites in the unit cell were evaluated, allowing an estimated lower limit |J |>0.1 cm⁻¹ for the exchange interaction between Cu(II) neighbors, consistent with the magnetic measurements. The observed angular variation of the line width is attributed to dipolar coupling between Cu(II) ions in the lattice.     

Effect of current sweep reversal on the magnetic field stability for a Bi-2223 superconducting solenoid

The effect of current sweep reversal on the temporal drift in magnetic field intensity for a Bi-2223 solenoid was investigated by experiment and using numerical simulation. Current sweep reversal, by as small as 1% of the peak current, was found to stabilize the drift in magnetic field intensity for a Bi-2223 tape solenoid. The field drift was due to flux creep in the Bi-2223 tape and the current sweep reversal formed a barrier for flux entrance at the upper and lower surface of the conductor, preventing flux creep. With a current reversal of several% of the peak current, the barrier formation extended over half of the solenoid and the magnetic field intensity became constant with time. The current sweep reversal technique should prove useful to stabilize an ultra-high field low/high-temperature superconducting nuclear magnetic resonance magnet operated at frequencies (field intensities) beyond 1 GHz (23.5 T).     

Optical absorption, EPR, infrared and Raman spectral studies of clinochlore mineral

Optical absorption, EPR, Infrared and Raman spectral studies have been carried out on natural clinochlore mineral. The optical absorption spectrum exhibits bands characteristic of Fe²⁺ and Fe³⁺ ions. A band observed in the NIR region is attributed to an intervalence charge transfer (Fe²⁺-Fe³⁺) band. The room temperature EPR spectrum of single crystal of clinochlore mineral reveals the dominance of Fe³⁺ ion exhibiting resonance signals at g=2.66; 3.68 and 4.31 besides one isotropic resonance signal at g=2.0. The EPR studies have been carried out for a polycrystalline sample in the temperature range from 103 to 443 K and for a single crystal of clinochlore mineral in the temperature range 123-297 K. The number of spins (N) participating in resonance at g=4.3 signal of the single crystal of clinochlore mineral has been calculated at different temperatures. The paramagnetic susceptibility (χ) is calculated from the EPR data at different temperatures for single crystal of clinochlore mineral. The Curie constant and Curie temperature values are evaluated from 1/χ versus T graph. The infrared spectral studies reveal the formation of Fe³⁺-OH complexes due to the presence of higher amount of iron in this mineral. The Raman spectrum exhibits bands characteristic of Si-O-Si stretching and Si-O bending modes.     

DC-60 heavy ion cyclotron complex: The first beams and project parameters

The construction of the DC-60 Heavy Ion Cyclotron for the Interdisciplinary Scientific Research Complex (ISRC) in Astana started in early 2004. The cyclotron was manufactured and tested at the Flerov Laboratory of Nuclear Reactions (FLNR) in Dubna. The main units were delivered to Astana and assembled in the ISRC building in the summer of 2006. The cyclotron was turned on in September, 2006. The first heavy ion beams in the whole A/Z and energy ranges were accelerated and extracted in December, 2006. The complex, based on the DC-60 cyclotron, is intended for applied and fundamental research using accelerated heavy ion beams ranging from Carbon to Xenon with energies in the range of 0.34–1.77 MeV/nucleon, as well as for experiments on the channel of low energy ion beams, where the ion extraction voltage supplied by the ECR source reaches 25 kV. The energy variation of the accelerated ions is accomplished by changing the ion charge. The possibility of smoothly tuning the ion energy by ±30% of its nominal value can be seen by changing the cyclotron magnetic field. Within the framework of commissioning the DC-60 cyclotron, a number of experiments were carried out with accelerating charged particle beams in the main points of the working diagram

Structural characterisation of [Cu2(bptd) (H2O) Cl4] and [Ni2(bptd)2(H2O)4] Cl4·3H2O; evidence of null intramolecular exchanges by EPR and magnetic measurements

Using the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (bptd), we recently prepared [Cu₂(bptd) (H₂O) Cl₄] and [Ni₂(bptd)₂ (H₂O)₄] Cl₄, 3H₂O in which the magnetic centres are connected through one diazine+one chloro and two diazine ligand bridges, respectively. These two compounds are the first examples that show null intramolecular magnetic interactions despite M-M distances close to 3.7 Å within perfectly planar edifices:Down to , [Cu₂(bptd)Cl₄(H₂O)] is paramagnetic while, below T_t, half of the Cu²⁺ions interact, leading to residual paramagnetism of one Cu²⁺/f.u. Magnetic susceptibility measurements, EPR and pulsed EPR study indicate the original intermolecular nature of AF exchanges.[Ni₂(bptd)₂(H₂O)₄]Cl₄·3H₂O susceptibility obeys a Curie-law involving pure paramagnetism. Moreover, its EPR spectrum can be interpreted on the basis of virtual S=1 monomers. Below 70 K, Zero Field Splitting (D∼275 G) due to dipolar interactions without magnetic exchanges could be responsible for the LT spectra splitting. For both compounds, the thia role is suggested as partially responsible for the null-in-plane magnetic exchanges.     

Magnetic material arrangement in oriented termites: a magnetic resonance study

Temperature dependence of the magnetic resonance is used to study the magnetic material in oriented Neocapritermes opacus (N.o.) termite, the only prey of the migratory ant Pachycondyla marginata (P.m.). A broad line in the g=2 region, associated to isolated nanoparticles shows that at least 97% of the magnetic material is in the termite’s body (abdomen + thorax). From the temperature dependence of the resonant field and from the spectral linewidths, we estimate the existence of magnetic nanoparticles 18.5 ± 0.3 nm in diameter and an effective magnetic anisotropy constant, K_eff between 2.1 and 3.2 × 10⁴ erg/cm³. A sudden change in the double integrated spectra at about 100 K for N.o. with the long body axis oriented perpendicular to the magnetic field can be attributed to the Verwey transition, and suggests an organized film-like particle system.     

Dielectric behavior,conduction and EPR active centres in BiVO4 nanoparticles

Bismuth vanadate (BiVO₄) nanomaterials were synthesized by mechano-chemical ball milling method and complementary investigations were devoted to their structures, nanoparticle morphologies and electronic active centres. The dielectric and conductivity behaviour were analysed systematically in wide temperature and frequency ranges to correlate such physical responses with the peculiarities of the samples. Large interfacial polarisations favoured by high specific surfaces of nanoparticles account for a drastic enhancement of the dielectric function in the quasi-static regime. Exhaustive analyses of the dielectric experiments were achieved and account for the main features of dielectric functions and their related relaxation mechanisms. The electrical conductivity is thermally activated with energies in the range 0.1–0.6 eV depending on the sample features. DC conductivity up to 10^–3 S/cm was obtained in well crystallized nanoparticles. Vanadium ions reduction was revealed by EPR spectroscopy with higher concentrations of the active centres (V⁴⁺) in more agglomerated and amorphous nanopowders. The EPR spectral parameters of V⁴⁺ were determined and correlated with the local environments of reduced vanadium ions and the characteristics of their electronic configurations. An insight is also made on the role of active electronic centres (V⁴⁺) on the conduction mechanism in nanostructured BiVO₄.     

Radiation stabilization of U5+ in CaO matrix and its thermal stability: Electron paramagnetic resonance and thermally stimulated luminescence studies

Electron paramagnetic resonance (EPR) evidence is presented for the radiation stabilization of pentavalent uranium in CaO matrix. From the theoretical predictions ofg value for U⁵⁺ in axial symmetries, it was concluded that U⁵⁺ at Ca²⁺ site is associated with a second neighbour charge compensating Ca²⁺ vacancy. EPR measurements also revealed the presence of Mn²⁺, Mn⁴⁺ and Cu²⁺ impurities in the samples. The thermal stability of U⁵⁺ was investigated using EPR and thermally stimulated luminescence (TSL) techniques. The TSL and EPR studies on gamma irradiated uranium doped calcium oxide samples had shown that the intense glow peak at 540 K is associated with the reduction in the intensity of EPR signal of U⁵⁺ ion around this temperature. This peak is associated with the process U⁵⁺+hole→U^6+*→U⁶⁺+hv. The activation energy for this process was determined to be 1.4eV.     

Time evolution of initially localized states in two-dimensional quantum dot arrays in a magnetic field

The evolution of non-stationary localized states |Ψ(t=0) is investigated in two-dimensional tight binding systems of N potential wells with and without a homogeneous field perpendicular to the plane. Most results are presented in analytical form, what is almost imperative if the patterns are as complex as for rings in a magnetic field, where the qualitatively different features arise depending on rational or irrational numbers. The systems considered comprise finite linear chains (N=2,3), finite rings (N=3–6), infinite chains, finite rings (N=3–6) in a magnetic field, and rings with leads attached to each ring site. The position of the particle at time t is described by the projection of the wave function P_m(t)=|m|Ψ(t)|² onto the localized basis function at site m. For finite chains and rings with N=3,4,6 the time evolution is periodic, whereas it is non-periodic for N=5 and N greater then 6. Rings in a magnetic field show a rich spectrum of different features depending on N and the number of flux quanta through the ring, including periodic oscillation and rotation of the charge as well as non-periodic charge fluctuations.     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

EPR investigation of two types of Syrian's natural zeolites

Two different samples of natural zeolite have been investigated by X-band electron paramagnetic resonance (EPR) spectroscopy. The observed EPR spectra are typical to those observed for Fe³⁺ and Mn²⁺ ions. The lines, related to the iron, are observed, respectively at g≈4.3 and g≈2. The observed six lines, at g≈2, are the hyperfine structure due to the Mn²⁺ ions. The simulation of the experimental EPR spectra suggests that both of the manganese and the iron are present in more one site. The temperature dependence of the EPR spectra has been also investigated. The nature of the different sites involved in the EPR absorption is discussed.     

Large magnetocaloric effect with a wide temperature range in Gd5Si4

Gd₅Si₄ magnets have attracted much attention due to their many appealing properties such as strong ferromagnetism, magnetovolume effect, and large reversal magnetocaloric effect (MCE). However, Gd₅Si₄ exhibits a relatively high Curie temperature (T_C ∼336 K) with a narrow refrigeration temperature span, which limits the refrigeration application at room temperature. Here we show that the T_C of Gd₅Si₄ can be reduced to 330 K and the phase transition temperature range can be effectively expanded by applying a high pressure of 6 GPa to the sample during heat treatment. In addition, the room-temperature magnetic entropy changes are improved and the refrigeration temperature span also becomes wider, which leads to an enhanced relative cooling power (RCP) of 748 Jkg^-1 under a magnetic field change of 5 T. These unique features indicate that the Gd₅Si₄ compound prepared under high pressure can serve as a magnetic refrigerant in a wide temperature range covering room temperature.