Effect of doping by boron,carbon, and nitrogen atoms on the magnetic and photocatalytic properties of anatase

The effect of doping of titanium dioxide with the anatase structure by boron, carbon, and nitrogen atoms on the magnetic and optical properties and the electronic spectrum of this compound has been investigated using the ab initio tight-binding linear muffin-tin orbital (TB-LMTO) band-structure method in the local spin density approximation explicitly including Coulomb correlations (LSDA + U) in combination with the semiempirical extended Hückel theory (EHT) method. The LSDA + U calculations of the electronic structure, the imaginary part of the dielectric function, the total magnetic moments, and the magnetic moments at the impurity atoms have been carried out. The diagrams of the molecular orbitals of the clusters Ti₃ X (X = B, C, N) have been calculated and the pseudo-space images of the molecular orbitals of the clusters have been constructed. The effect of doping on the nature and origin of photocatalytic activity in the visible spectral range and the specific features of the generation of ferromagnetic interactions in doped anatase have been discussed based on the analysis of the obtained data. It has been shown that, in the sequence TiO_{2 ? y} N _y → TiO_{2 ? y} C _y → TiO_{2 ? y} B _y (y = 1/16), the photocatalytic activity can increase with the generation of electronic excitations with the participation of impurity bands. The calculated magnetic moments for boron and nitrogen atoms are equal to 1 μ_B, whereas the impurity carbon atoms are nonmagnetic.     

Measurement of the nuclear magnetic dipole moment of Au197 and hyperfine structure measurements in the ground states of Au197, Ag107, Ag109 and K39

Using an atomic beam magnetic resonance apparatus the nuclear magnetic dipole momentμ _I of the stable isotope Au¹⁹⁷ was measured directly with the doublet method. The result isμ _I(Au¹⁹⁷)=0.143491 (9)μ _n, uncorrected for atomic diamagnetism. Further hyperfine structure measurements were performed in the ground states of K³⁹, Ag¹⁰⁷, Ag¹⁰⁹ and Au¹⁹⁷ with the following results:Δv(K³⁹)=461.719723 (38) MHzΔv(Ag¹⁰⁷)=1712.512111 (18) MHzΔv(Ag¹⁰⁹)=1976.932075 (17) MHzΔv(Au¹⁹⁷)=6099.320184 (13) MHzg _J(Ag¹⁰⁷)/g _J(K39)=1.0000260 (20)g _J(Au¹⁹⁷)/g _J(K39)=1.0005076 (20).     

Geometric,stability, and electronic properties of gold-doped Pd clusters (Pd<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>Au, <Emphasis Type="Italic">n</Emphasis> = 3~20)

The structure, stability, and electronic properties of Pd _n Au (n = 3~20) clusters are studied by density functional theory. The results show that the clusters studied here prefer three-dimensional structures even with very small atom number. It is found that the binding energies of Pd _n Au clusters are higher than the corresponding pure Pd _n clusters with the same atom number. Most Pd _n Au clusters studied here are magnetic with magnetic moments ranging from 1.0 to 7.0 μ _B. The dissociation energies of Pd atoms are lower than the doped gold atom, that is the doped Au atom will increase the mother clusters stability and activity.     

Structural and magnetic properties of Fe<Subscript>7−<Emphasis Type="Italic">n</Emphasis></Subscript>Pt<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> with <Emphasis Type="Italic">n</Emphasis> = 0, 1, 2, . . . 7, bimetallic clusters

An exhaustive study of the structural and magnetic properties of Fe_7?n Pt _n with n = 0, 1, 2, …7, bimetallic clusters is presented. Based on ab initio density functional theory that includes spin-orbit coupling (SOC) and graph theory, the ground state geometry, the local chemical order, and the orbital and spin magnetic moments are calculated. We show how the systems evolves from the 3-d Fe to the quasi-planar Pt clusters. These calculations show that SOC are necessary to describe correctly the composition dependence of the binding energy of these nanoalloys. We observe that the ground state geometries on the Fe rich side resemble the fcc structure adopted by bulk samples. Furthermore, we observe how the spin and orbital magnetic moments depend on the chemical concentration and chemical order. Based on these results, we estimated the magnetic anisotropy energy and found that the largest values correspond to some of the most symmetric structures, Fe₅Pt₂ and FePt₆. To determine the degree of non-collinearity, we define an index that shows that in FePt₆ the total magnetic moments, on each atom, are the less collinear.     

Effect of low-temperature annealing on the magnetization curve of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + <Emphasis Type="Italic">x</Emphasis></Subscript> ceramics

The effect of low-temperature annealing on the magnetization curve of YBa₂Cu₃O_{6 + x} ceramics in the superconducting state (x ≈ 0.9) is investigated. When the annealing time is fairly long, the field dependence of magnetic moment M exhibits a feature in the form of a plateau, where the value of M remains almost constant. The evolution of this feature in the magnetization curves of annealed samples with annealing time and temperature is studied. It is assumed that low-temperature annealing gives rise to metastable ferromagnetic clusters in YBa₂Cu₃O_{6 + x} ceramics, the contribution of which to the magnetic moment accounts for the feature in the magnetization curves of the annealed samples.     

Anomalous transport properties of a paramagnetic NiTiO<Subscript>3</Subscript> + HTSC two-phase system representing a random Josephson junction network

Composites representing a network of random Josephson junctions and characterized by the compositions 92.5 at. % Y_3/4Lu_1/4Ba₂Cu₃O₇+7.5 at. % NiTiO₃ and 92.5 at. % Y_3/4Lu_1/4Ba₂Cu₃O₇+7.5 at.% MgTiO₃ are synthesized, and their magnetoresistance properties are studied. The temperature dependence of the resistance R(T) measured for the composite that contains the paramagnetic NiTiO₃ compound exhibits a characteristic feature below the superconducting transition temperature T_c of the high-T_c superconductor, namely, a region where R is independent of the current j and weakly depends on the magnetic field H. Below a certain temperature T_m, a strong dependence of R on j and H is observed, which is peculiar to a network of Josephson junctions. The dependences R(T, j, H) obtained for the “reference” samples with the nonmagnetic MgTiO3 compound exhibit no such features. The anomalous behavior of the HTSC + NiTiO3 composite is explained by the effect produced by the magnetic moments of Ni atoms in the insulating barriers on the transport current.     

High-pressure effect on the crystal and magnetic structures of the frustrated antiferromagnet YMnO<Subscript>3</Subscript>

The high-pressure (to 5 GPa) effect on the crystal and magnetic structures of the hexagonal manganite YMnO₃ is studied by neutron diffraction in the temperature range 10–295 K. A spin-liquid state due to magnetic frustration on the triangular lattice formed by Mn ions is observed in this compound at normal pressure and T > T_N = 70 K, and an ordered triangular antiferromagnetic state with the symmetry of the irreducible representation Γ₁ arises at T < T_N. The high-pressure effect leads to a spin reorientation of Mn magnetic moments and a change in the symmetry of the antiferromagnetic structure, which can be described by a combination of the irreducible representations Γ₁ and Γ₂. In addition, it is observed that the ordered magnetic moment of Mn ions decreases from 3.27 μ_B (5 GPa) to 1.52 μ_B (5 GPa) at T = 10 K and diffuse scattering is enhanced at temperatures close to T_N. These effects can be explained within the model of the coexistence of the ordered antiferromagnetic phase and the spin-liquid state, whose volume fraction increases with pressure due to the enhancement of frustration effects.     

Magnetic polarons,clusters, and their effect on the electric properties of weakly doped lanthanum manganites

The resistivity, magnetoresistance, thermopower, and magnetic susceptibility of La_1?xA_xMnO₃(A≡Ca,Sr;x=0.07–0.1) single crystals are investigated in the temperature range from 77 to 400 K. Sharp changes in the properties (the resistivity activation energy ΔEρ, its temperature coefficient γ, the thermopower activation energy ΔE _S , the magnetoresistance, and the appearance of spontaneous magnetization) of these crystals occur near a temperature of 275±25 K, which is approximately twice as high as their Curie point T_C and approximately half of the structural transition temperature. The results are explained by the phase separation: the formation of ferromagnetic clusters. The phase separation occurs through the coalescence of small-radius unsaturated magnetic polarons, in which only two or three magnetic moments of Mn are polarized, into a large-radius ferromagnetic polaron (a cluster about 10–12 Å in size) with several charge carriers. As a result, the short-range order occurs in the cluster at a temperature of about 275 K, which is close to T _C of conducting doped manganites. The results of the experimental studies of the resistivity and the magnetoresistance as functions of temperature and magnetic field and the estimates agree well with the cluster model.     

Mechanism of carrier generation and the origin of the pseudogap and 60 K phases in YBCO

The mechanism of hole carrier generation is considered in the framework of a model assuming the formation of negative U centers (NUCs) in HTSC materials under doping. The calculated dependences of carrier concentration on the doping level and temperature are in quantitative agreement with experiment. An explanation is proposed for the pseudogap and 60 K phases in YBa₂Cu₃O_6+δ. It is assumed that a pseudogap is of superconducting origin and arises at temperature T* > T_c∞ > T_c in small nonpercolating clusters as a result of strong fluctuations in the occupancy of NUCs (T_c∞ and T_c are the superconducting transition temperatures of an infinitely large and finite NUC clusters, respectively). The T*(δ) and T_c(δ) dependences calculated for YBa₂Cu₃O_6+δ correlate with experimental dependences. In accordance with the model, the region between T*(δ) and T_c(δ) is the range of fluctuations in which finite nonpercolation clusters fluctuate between the superconducting and normal states due to NUC occupancy fluctuations.     

Dependence of the heat capacity of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites on the Ag content

The heat capacity of La_1?x Ag _x MnO₃ manganites with x = 0.1, 0.15, and 0.2 is measured in the temperature range 77–350 K. An analogy between the effect of doping and the effect of a magnetic field on the temperature dependence of heat capacity of the La_1?x Ag _x MnO₃ system is revealed. As lanthanum is replaced by silver, the volume fraction of the ferromagnetic phase increases, while, in the paramagnetic state, the Jahn-Teller distortions are eliminated. The results of the aforementioned measurements suggest that the phase transition near the Curie point is caused by the competition between the Coulomb and exchange electrostatic interactions. The comparison of the concentration dependences of T _C for La_1?x Sr _x MnO₃ and La_1?x Ag _x MnO₃ points to good potentialities of the latter system from the viewpoint of applications.     

Structural features and the microscopic dynamics of the three-component Zr<Subscript>47</Subscript>Cu<Subscript>46</Subscript>Al<Subscript>7</Subscript> system: Equilibrium melt,supercooled melt,and amorphous alloy

The structural and dynamic properties of the three-component Zr₄₇Cu₄₆Al₇ system are subjected to a molecular dynamics simulation in the temperature range T = 250–3000 K at a pressure p = 1.0 bar. The temperature dependences of the Wendt–Abraham parameter and the translation order parameter are used to determine the glass transition temperature in the Zr₄₇Cu₄₆Al₇ system, which is found to be T_c ≈ 750 K. It is found that the bulk amorphous Zr₄₇Cu₄₆Al₇ alloy contains localized regions with an ordered atomic structures. Cluster analysis of configuration simulation data reveals the existence of quasi-icosahedral clusters in amorphous metallic Zr–Cu–Al alloys. The spectral densities of time radial distribution functions of the longitudinal (C?_L(k, ω)) and transverse (C?_T(k, ω)) fluxes are calculated in a wide wavenumber range in order to study the mechanisms of formation of atomic collective excitations in the Zr₄₇Cu₄₆Al₇ system. It was found that a linear combination of three Gaussian functions is sufficient to reproduce the (C?_L(k, ω)) spectra, whereas at least four Gaussian contributions are necessary to exactly describe the (C?_T(k, ω)) spectra of the supercooled melt and the amorphous metallic alloy. It is shown that the collective atomic excitations in the equilibrium melt at T = 3000 K and in the amorphous metallic alloy at T = 250 K are characterized by two dispersion acoustic-like branches related with longitudinal and transverse polarizations.     

Hyperfine nuclear interaction at copper lattice sites of high-temperature superconductors studied by <Superscript>61</Superscript>Cu(<Superscript>61</Superscript>Ni) Mössbauer emission spectroscopy

Mössbauer emission spectroscopy on the ⁶¹Cu(⁶¹Ni) isotope has been used to determine the quadrupole coupling constant C(Ni) and magnetic induction B(Ni) for the ⁶¹Ni²⁺ probe at copper sites in Cu₂O, CuO, La_{2 ?x}Ba_xCuO₄, Nd_2?xCe_xCuO₄, RBa₂Cu₃O₆, and RBa₂Cu₃O₇ (R=Y, Nd, Gd, Yb). The compounds containing divalent copper were found to exhibit linear C(Ni) vs. C(Cu) and B(Ni) vs. B(Cu) relations [C(Cu) and B(Cu) are the quadrupole coupling constant and magnetic induction for the ⁶³Cu probe, respectively, found by NMR], which is interpreted as an argument for the copper being in divalent state. The deviation of the data points corresponding to the Cu(1) sites in RBa₂Cu₃O₆ and RBa₂Cu₃O₇ from the C(Ni) vs. C(Cu) straight line may be due either to the copper valence being other than 2+ (in the RBa₂Cu₃O₆ compounds) or to the principal axes of the total and valence electric field gradient being differently oriented (in the RBa₂Cu₃O₇ compounds).     

Penetration of a magnetic field into the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−δ</Subscript> high-temperature superconductor: Magnetoresistance in weak magnetic fields

The penetration of a magnetic field into superconducting grains and weak links of YBa₂Cu₃O_7?δ ceramic high-temperature superconductors is investigated using measurements of the transverse and longitudinal magnetoresistances at T=77.3 K and 0≤H≤～500 Oe as a function of the transport current in the range ～0.01≤I/I _c ≤～0.99. The effects associated with the complete penetration of Josephson vortices into weak links of the high-temperature superconductor in magnetic fields H_c2J, the onset of penetration of Abrikosov vortices into superconducting grains in magnetic fields H_c1A, and the first-order transition from the Bragg glass phase to the vortex glass phase in fields H_BG-VG are revealed and interpreted. The I-H phase diagrams YBa₂Cu₃O_7?δ high-temperature superconductors are constructed for I ⊥ H and I ‖ H.     

Magnetic anisotropy of Co/Cu/Co films with indirect exchange coupling

The effect of isothermal annealing on the magnetic anisotropy, bilinear and biquadratic exchange coupling energies, and domain structure of Co/Cu/Co trilayer fiilms with d_Co=6 nm and d_Cu=1.0 and 2.1 nm prepared by magnetron sputtering has been studied. It is shown that, under isothermal annealing, the biquadratic coupling energy decreases by more than an order of magnitude in films with d_Cu=1.0 nm and increases in films with d_Cu=2.1 nm. The fourth-order magnetic anisotropy is shown to be related to the existence of biquadratic exchange energy.     

Level-crossing-Untersuchung der Hyperfeinstruktur des 3d 10 4p 2 P 3/2-Terms von Cu63 und Cu65

The level-crossing technic has been used to investigate the hyperfinestructur of the 3d ¹⁰ 4p ² P _3/2-term in Copper I by scattering the resonance line λ=3248 Å on an atomic beam of separated isotop Cu⁶³ respectively Cu⁶⁵ in an external magnetic field. From the level-crossing signals values for the magnetic dipol interaction constantsA and for the electric quadrupol interaction constantsB are deduced to beeA(Cu⁶³)=(194,72±0,15) Mc/secB(Cu⁶³)=?(28,8±0,6) Mc/secA(Cu⁶⁵)=(208,57±0,15) Mc/secB(Cu⁶⁵)=?(25,9±0,6) Mc/sec. With theA-value of the 3d ¹⁰ 4p²P_1/2-term from optical measurements the ratioA(² P _3/2)∶A(² P _1/2)≈0,4 is about twice greater than for an unperturbetalkali-like²P-term. From the width of the level-crossing signals a mean lifetime of the 3d¹⁰ 4p²P_3/2-term τ=(7,0±0,2) · 10^?9 sec is deduced.     

Colossal room-temperature magnetoresistance in thin La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript>y</Subscript>MnO<Subscript>3</Subscript> epitaxial films

The first thin La_1?xAg_yMnO₃ epitaxial films (_y ≤ x) were grown on SrTiO₃ (110) substrates with silver present in the ionized state (Ag⁺) only. The Curie temperatures T_C of the compositions with x = y = 0.05, x = y = 0.1, and x = 0.3 and y = 0.27 crystallizing in the hexagonal structure \(R\bar 3c\) above or close to room temperature. The temperature dependences of electrical resistivity ρ and of magnetoresistance ¦Δρ/ρ/¦ = ¦(ρ_H ? ρ _H = 0)/ρ_H=0¦ pass through maxima near T_C, with the magnetoresistance being negative and reaching colossal values of ～7–20% in a magnetic field H = 8.2 kOe not only at T_C but also at room temperature. The magnetic moment per formula unit as derived from the saturation magnetization at T = 5 K is substantially smaller than expected for complete ferromagnetic ordering. The magnetization in fields of up to 6 kOe depends on the actual sample cooling conditions, and the hysteresis loop of a field-cooled sample is displaced along the H axis by ΔH. The above properties can be accounted for by the fact that the films are in a two-phase magnetic (ferromagnetic-antiferromagnetic) state induced by strong s-d exchange. The maximum value of Δ H was used to calculate the energy of exchange coupling between the ferromagnetic and antiferromagnetic parts of a sample.     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

Electron and nuclear magnetic resonances associated with magnetoelectric and antiferroelectric interactions in the exchange-noncollinear (“square”) chiral antiferromagnet Nd<Subscript>2</Subscript>CuO<Subscript>4</Subscript> and their behavior in chiral phase transitions

Experiments with the tetragonal antiferromagnet Nd₂CuO₄ in the temperature range 1.5 K < T < T _N = 245 K show that the magnetic moments of Cu²⁺ possess an exchange-noncollinear magnetic structure of the “square” type, which has the form of an exchange doublet whose components exhibit different chiralities (Γ₄ and Γ₅ phases). Between these phases, consecutive phase transitions Γ₄ ? Γ₅ ? Γ₄ with a change in chirality take place at temperatures T₁ = 30 K and T₂ = 70 K. The electron and nuclear magnetic resonances (natural frequencies and susceptibilities) associated with excitation of magnons (due to the magnetoelectric and antiferroelectric interactions) by an ac electric field E(t), as well as a variable magnetic field H(t) applied in the case of a constant electric field E⁰, are calculated. It is predicted that nuclear magnetic resonance is excited by an ac electric field at frequencies determined by hyperfine fields of the sublattices. The change in the resonance frequencies upon the above chiral phase transitions are analyzed (being first-order phase transitions, these transitions possess a number of features associated with the chirality of the magnetic structures).     

Improved Scaling of the Magnetic Heat Capacity in La<Subscript>0.85</Subscript>Ag<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> Manganite

The heat capacity in a La_0.8 Ag_0.15 MnO₃ manganite has been measured near the Curie temperature T _C in applied magnetic fields up to 26 kOe to study the scaling critical behavior and to obtain the universality class. The conventional scaling fails in application to the manganites with a hysteresis and the strong sensitivity of T _C to a magnetic field. However, the application of the improved scaling procedure designed by us allows yielding the good scaling the magnetic heat =0.23 capacity in La_0.85Ag_0.15MnO₃, which may belong to a new universality class for systems with the strong spin-orbital coupling of t _2g -electrons, namely, double -Heisenberg with the critical exponent of the heat capacity α = ?0.23 and the critical exponent of the correlation radius v=0.7433. This new universality class is consistent with the crystal, magnetic and orbital symmetries for the La_0.85Ag_0.15MnO₃. Scaling failure in the vicinity of T _C in the range of t/H ^1/2ν ≈ [?0.033;0.024] is understood by finite-size and other disordering effects when T →T _C. It is remarkable that finite-size effect is consistent with grain size, L ≈ 50 μm, in the La_0.85Ag_0.15MnO₃. The correlation radius, Lt ^ν ≈ 30.28 Å, estimated from the finite-size effect is of the same order of magnitude with the sizes of the ferromagnetic fluctuations and drops in manganites.     

Magnetic phase transitions in Nd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

The magnetic properties of manganites of the Nd_1?xCa_xMnO₃ system with x≤0.15 have been studied. It is shown that, in the 0.06≤x≤0.1 interval, the results can be interpreted using a model according to which the concentrational transition from a weakly ferromagnetic (WFM) state (x=0) to a ferromagnetic (FM) state (x>0.15) proceeds via a mixture of the exchange-coupled FM and WFM phases. In the vicinity of T=9 K, samples with 0.06≤x≤0.1 exhibit a spontaneous magnetic phase transition involving reorientation of the magnetization vectors of the WFM and the exchange-coupled FM phases. In the temperature interval between 5 and 20 K, a sample with the composition Nd^0.92Ca^0.08MnO^2.98 exhibits metamagnetic behavior. Magnetic phase diagrams in the H?T and T?x coordinates are presented. The appearance of the spin-reorientation transitions is explained in terms of the magnetic analog of the Jahn-Teller effect with allowance for the fact that, according to the neutron diffraction data, the magnetic moments of neodymium ions in the FM phase are parallel to the magnetic moments of manganese ions.