EPR Application in the Study of K3\text{}_{3}H(SO4\text{}_{4})2\text{}_{2} Proton Conductor Doped with Mn2+\text{}^{2+} or VO2+\text{}^{2+} Ions

The EPR of Mn$\text{}^{2+}$- or VO$\text{}^{2+}$-doped superprotonic conductor K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ is studied in the 80-471 K temperature range. VO$\text{}^{2+}$ EPR spectrum reveals diffusion induced merging of proton transferred superhyperfine structure above 380 K. Line width anomaly is observed in Mn$\text{}^{2+}$ EPR spectrum which is attributed to the intrabond and interbond proton motions, these lead to high protonic conductivity. It is shown that paramagnetic centers namely of electronic spin greater than 1, with excess charge compensated by the protonic vacancy, are good probes to monitor the protonic conductivity on molecular level

Pretransition Phenomena in Fast-Proton Conductors

In this paper we present recent experimental results related to nonlinear crystal field fluctuations and current flow in K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ fast-proton conductor far below the transition temperature T$\text{}_{g}$. The results for crystalline and powdered samples are quantitatively explained in the framework of soliton model of charge transport

EPR Study of Cu2+\text{}^{2+} Doped Fast-Proton Conductor K3\text{}_{3}H(SO4\text{}_{4})2\text{}_{2} in the Temperature Range 100-450 K

The K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ doped with Cu$\text{}^{2+}$ ion was studied in detail by X-band CW EPR. Two kinds of Cu$\text{}^{2+}$ complexes (magnetically and structurally nonequivalent) denoted as Cu$\text{}^{2+}$(I) and Cu$\text{}^{2+}$(II) were found. Spin-Hamiltonian parameters, direction cosines, and coordination of Cu$\text{}^{2+}$ ion were determined at room temperature. The superhyperfine structure was observed below 250 K as a result of interacting of Cu$\text{}^{2+}$ ion with four equivalent protons (I=1/2). Temperature studies of K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ crystal show that interbond motion as a precursor of superprotonic phase transition occurs at above≈250 K

INFLUENCE OF SPONTANEOUS POLARIZATION ON THE EPR SPECTRA OF Cr3+ IONS IN TGFB

Le spectre EPR de l'ion Cr3+ du TGFB est étudié en fonction de la température au voisinage du point de Curie. Au-dessus du point de Curie, le champ cristallin agissant sur l'ion Cr3+ montre que la symétrie est cubique tandis qu'au-dessous du point de Curie la polarisation spontanée perturbe le champ cristallin cubique et la symétrie devient rhombique.The EPR spectrum of Cr3+ ion in TGFB was examined versus temperature near the Curie point. Above the Curie point the crystal field acting on Cr3+ ion indicate the Cubic symmetry whereas below the Curie point the spontaneous polarization disturbs the Cubic crystal field and the symmetry becomes rhombic

Investigations of Phase Transitions in (NH4\text{}_{4})3\text{}_{3}H(SO4\text{}_{4})2\text{}_{2} Crystal by Means of Mn2+\text{}^{2+} EPR Spectra

EPR of Mn$\text{}^{2+}$ impurity ion in the (NH$\text{}_{4}$)$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ crystal is studied in the temperature range 80-420 K. It is shown that Mn$\text{}^{2+}$ substitutes NH$\text{}_{4}^{+}$(I) ion and is coordinated in deformed oxygen octahedron in which takes two "off-center" positions. Its spin-Hamiltonian parameters and direction cosines of crystal field are determined. The successive EPR line splitting for three phase transitions is discussed

EPR Study of Monoclinic RbD2\text{}_{2}PO4\text{}_{4} Monocrystal Doped with Cr5+\text{}^{5+} Ion

Deuterated monoclinic RbD$\text{}_{2}$PO$\text{}_{4}$ (DRDP) doped with chromium Cr$\text{}^{5+}$ is studied by EPR in 90 K to 400 K temperature range. EPR reveals two types of paramagnetic centers: single Cr$\text{}^{5+}$ (S = 1/2) complex and Cr$\text{}^{5+}$-Cr$\text{}^{5+}$ coupled pairs with effective spin S = 1. The EPR line splitting of single Cr$\text{}^{5+}$ complex in DRDP versus temperature agrees with the unit cell multiplication. The splitting of EPR line of pair spectrum appears at T* = 160 K, far below the phase transition temperatures and is due to the anisotropy of the exchange interaction. The clustering effect in the low-dimensional DRDP is suggested

EPR Study of Cu 2+

The K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ doped with Cu$\text{}^{2+}$ ion was studied in detail by X-band CW EPR. Two kinds of Cu$\text{}^{2+}$ complexes (magnetically and structurally nonequivalent) denoted as Cu$\text{}^{2+}$(I) and Cu$\text{}^{2+}$(II) were found. Spin-Hamiltonian parameters, direction cosines, and coordination of Cu$\text{}^{2+}$ ion were determined at room temperature. The superhyperfine structure was observed below 250 K as a result of interacting of Cu$\text{}^{2+}$ ion with four equivalent protons (I=1/2). Temperature studies of K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ crystal show that interbond motion as a precursor of superprotonic phase transition occurs at above≈250 K

EPR Study of VO2+\text{}^{2+} Center in Fast Proton Conductor K3\text{}_{3}H(SO4\text{}_{4})2\text{}_{2}

The pretransitional phenomena of superprotonic phase transition (T$\text{}_{sp}$=471 K) were studied in detail by X-band continuous wave EPR spectra of K$\text{}_{3}$H(SO$\text{}_{4}$)$\text{}_{2}$ crystal doped with VO$\text{}^{2+}$ ions. Three kinds of VO$\text{}^{2+}$ complexes (magnetically equivalent but structurally non-equivalent) denoted as VO$\text{}^{2+}$(I), VO$\text{}^{2+}$(II), and VO$\text{}^{2+}$(III) were found. "Smearing out" of the superhyperfine structure was observed as a result of interbond proton motion. VO$\text{}^{2+}$ impurity replaces K$\text{}^{+}$ ion and experiences the same average crystal field gradient at T$\text{}_{sp}$=471 K for I- and II-type complexes. The increase in interbond proton frequency hopping above 360 K is a reason of significant line broadening

Magnetic Properties in Mn Pure Powder

The structural and magnetic properties of deformed powder of Mn obtained by mechanical grinding have been investigated using X-ray diffraction and magnetic measurements. The small values of ferromagnetic moment of Mn after grinding are attributed to the formation of a deformed phase at the surface of grains with enlargement of the interatomic spacings at the grains boundaries

Microwave X-Band Resonances in Doped Cd₂Nb₂O₇ Monocrystals

Cadmium pyroniobiate (CNO) is the ferroic material with unusual diffuse phase diagram which includes both relaxor and nanocluster domains. We present the data for CNO crystals with several admixtures of paramagnetic ions studied on X and S microwave bands at zero-external magnetic field and classical EPR conditions. Our results lead to an assertion of a ferroelectric resonance effect due to "electronic ferroelectricity". The data fit well to the Falicov-Kimball theoretical model applicable to strongly-correlated-electron or mixed-valence systems