An EPR Study of Superoxide Radicals from Potassium Superoxide Solutions

Electron paramagnetic resonance spectroscopy and the spin trapping technique were employed in order to monitor the superoxide radical liberated from potassium superoxide in aqueous alkaline solutions; DEPMPO (5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide) was used as a trapping agent. Three reaction systems were prepared, varying the ratios between KO₂, superoxide and DEPMPO. The data indicate distinct mechanisms leading to DEPMPO/spin adducts with different kinetic rates.     

Amphoteric exciton trapping by 3d-impurities in A2B6 semiconductors

It is shown that the neutral deep level state of transition metal impurity in A₂B₆ semiconductors plays a role of amphoteric localization centre for the excitons: it can capture either electron or hole to the d-shell leaving either hole or electron in a loosely bound hydrogenlike orbit respectively. The physical properties of both excitonic states are compared and the possibility to interpret in these terms the optical spectra of ZnS(Se) doped by Ni and Co is discussed.     

Hierarchy of percolation thresholds and the mechanism for reduction of magnetic moments of transition metals intercalated into TiSe<Subscript>2</Subscript>

The concentration dependences of the effective magnetic moment of transition metal atoms intercalated into TiSe₂ are analyzed in the framework of the percolation theory. It is shown that, depending on the degree of localization of impurity states, the effective magnetic moment is determined by the overlap of 3d orbitals of transition metals or orbitals of titanium atoms coordinated by impurity atoms.     

Theoretical study of magnetic ordering and electronic properties of AgxAl1−x N compounds

Ferromagnetic ordering of silver impurities in the AlN semiconductor is predicted by plane-wave ultrasoft pseudopotential and spin-polarized calculations based on density functional theory (DFT). It was found that an Ag impurity atom led to a ferromagnetic ground state in Ag_0.0625Al_0.9375N, with a net magnetic moment of 1.95 μ_B per supercell. The nitrogen neighbors at the basal plane in the AgN₄ tetrahedron are found to be the main contributors to the magnetization. This magnetic behavior is different from the ones previously reported on transition metal (TM) based dilute magnetic semiconductor (DMS), where the magnetic moment of the TM atom impurity is higher than those of the anions bonded to it. The calculated electronic structure band reveals that the Ag-doped AlN is p-type ferromagnetic semiconductor with a spin-polarized impurity band in the AlN band gap. In addition, the calculated density of states reveals that the ferromagnetic ground state originates from the strong hybridization between 4d-Ag and 2p-N states. This study shows that 4d transition metals such as silver may also be considered as candidates for ferromagnetic dopants in semiconductors.     

μ−SR studies of high-T c oxide-superconductor systems

Application of negative muons to studies of electronic states at oxygen sites of high-T _c copper-oxide superconductors as well as 3d transition metal oxides are described. A characteristic feature of the muonic oxygen probes in oxides is discussed. Muonic oxygen can be considered as a nitrogen impurity in the oxides. Around muonic oxygen one hole seems to be introduced and the behavior of the hole depends on the properties of the host oxides. A new impurity problem in strongly correlated electron systems is formulated.     

Mo¨ssbauer study of iron sulfides doped with 3d-transition metals

It is found by Mo¨ssbauer measurements on M_0.025Fe_0.975S (M=Sc, Ti, V, Cr, Mn, Co, Ni, Cu) that the 3d-transition metal impurities profoundly affect both the crystallographic and spin rotation transitions of iron sulfide.It is noteworthy that both V_0.025Fe_0.975S and Co_0.025Fe_0.975S have Morin transition temperatures T_M which are distinctly different from that of FeS; furthermore, the directions of changes of T_M are opposite for V_0.025Fe_0.975S and Co_0.025Fe_0.975S.A vanadium impurity of 2.5% of the metal atoms in the iron sulfide makes the crystallographic transition take place rapidly in a narrow temperature region of about 15 K, while the α transition in FeS takes place over a wide temperature range of about 200 K.It is also found that the α transition for V_0.025Fe_0.975S has a hysteresis width of 5 K.     

Origin of the structural local transition in the molecular impurity ion MnO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> in the K<Subscript>3</Subscript>Na(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript> ferroelastic

A new model is proposed for a local transition in a Jahn-Teller impurity center in a crystal with a ferroelastic (ferroelectric) phase transition. This model is based on direct interaction of the order parameter of the phase transition in the matrix with the Jahn-Teller impurity degrees of freedom. It is shown that, under these conditions, the order parameter field can induce lifting of degeneracy of the electronic states active in the Jahn-Teller effect, which is accompanied by a transition from the Jahn-Teller effect to the pseudo-Jahn-Teller effect with its subsequent suppression. As a result, a decrease in temperature gives rise to a structural local transition in the region of the low-symmetry ferroelastic (ferroelectric) matrix phase from the many-well local adiabatic to a single-well potential. The model proposed allows interpretation of experimental data obtained in an EPR study of the molecular impurity ion MnO ₄ ^2? in the K₃Na(CrO₄)₂ ferroelastic.     

An NMR Analysis of Transitions in FexNbxV2-2xO4

The first order semiconductor - metall phase transition with the lattice symmetry change from monoclinic to tetragonal and the conductivity jump of several orders of magnitude is observed in pure vanadium dioxide and the dioxide doped by varios impurities [I]. Transition temperature T_t for pure VO₂ is 68°C and depends on the impurity. For example, the impurities which enter the insulating phase as pentavalent ions Nb⁵⁺ [2] give rise to a decrease in metal-semiconductor transition temperature at low concentrations and the trivalent ions Cr³⁺, Fe³⁺ [3,4] lead to an increase in T_t. In the latter case three different monoclinic phases are stabilized at a temperature below T_t. It has been already shown [5] that for double doping of vanadium dioxide by pentavalent Nb⁵⁺ and trivalent Fe³⁺ or Cr³⁺ ions three semiconductor phases exist (M_I, M₂, M₃) but the transition temperature decreases as the impurity concentration increases.     

Electronic structure of magnetic and non-magnetic substitutional 3d transition metal impurities in germanium

The electronic structure around the ideal 3d transition metal impurities at substitutional site of germanium is calculated self-consistently within the local density formalism. Chemical trend of 3d impuritiy levels caused by the strong p-d hybridization, is revealed in the case of non-magnetic state. The magnetic state of the iron impurity is also presented and the local magnetic moment experienced by iron impurity is calculated to be 3.72μ_B.     

<Emphasis Type="Italic">Ab initio</Emphasis> studies of the energy characteristics and magnetic properties of point defects in GaAs

The formation energies of intrinsic point defects and solution energies of transition metal impurities in gallium arsenide are determined on the basis of ab initio calculations using the method of a locally self-consistent Green’s function, which is a generalization of the coherent potential approximation. Based on the calculated energies, the conclusion is made that the As_Ga antisite defect is the most common intrinsic defect in GaAs. Calculations showed that transition metal impurities, except for Ni, preferentially occupy gallium sites substitutionally. The magnetic moments of impurity atoms are calculated as a function of the chemical environment. It is shown that, in compensated GaAs, Mn atoms tend to form clusters.     

Specific heat below 1k some examples in magnetism

The measurement of specific heat below 1 K by means of a quasi-adiabatic calorimeter, employing adiabatic demagnetization for cooling, is described. The lattice, hyperfine and electronic contributions in the temperature domain 0.05 < T < 4 K are discussed briefly as an introduction to the analysis and exploitation of the magnetic contribution to the specific heat in magnetic insulators. The comparison with simple magnetic models is illustrated by the analysis of the specific heat data of the NdMO₃ perovskites, with M = nonmagnetic atom. The action of a magnetic field, albeit an internal field, is discussed using NdMO₃, M = Fe, Cr and Ni perovskite as examples. Finally, two molecular magnetic materials are discussed; Gd₂(ox)[Cu(pba)]₃[Cu(H₂O)₅]· 20H₂O as a candidate for ferromagnetic order in a rare earth transition metal complex, and Gd(hfac)₃NITR, with the nitronyl nitroxide magnetic radical interacting with the rare earth.     

Fast Doping of Cu into ZnSe NCs by Hydrazine Promoted Cation Exchange in Aqueous Solution at Room Temperature

Controllable doping is an effective way of tuning the properties of semiconductor nanocrystals (NCs). In this work, a simple strategy of fast doping Cu ions into ZnSe NCs under ambient conditions was proposed. The principle of doping is based on hydrazine (N₂H₄) promoted cation exchange reaction. By direct addition of Cu ion stock solution into the preformed ZnSe NCs, Cu doped ZnSe NCs can be obtained. Furthermore, the emission of doped NCs can be tuned by changing the amount of impurity ion addition. The cation exchange reaction is facilitated by three factors: 1) N₂H₄ addition, 2) fast impurity ions, and 3) partial stabilizer removal. The proposed cation exchange reaction in aqueous solution could be an alternate route for NC doping as well as synthesis of ionic NCs.     

Ab initio calculations of electric field gradients detected by impurities in TiO2, Al2O3 and CaCO3

We present ab initio calculations of electric field gradients (EFGs) at impurity sites in ionic crystals TiO₂, Al₂O₃ and CaCO₃. The electronic structure was calculated self-consistently by the KKR method in the framework of the local spin density approximation of the density functional theory. The system with a single impurity was simulated by the super cell method. It was found that EFGs for the transition metal impurities (Sc, Nb, Cd and Ta) in TiO₂ were well reproduced by the calculations if the charge state of them in TiO₂ was taken into account. The present method was applied to the determination of the implantation sites of N and O nuclei in TiO₂. The calculation of EFGs at a Si impurity in Al₂O₃ and at Ca site in CaCO₃ were used to derive the quadrupole moments of ²⁷Si and ³⁹Ca from their quadrupole coupling constants. This revised version was published online in August 2006 with corrections to the Cover Date.     

Absence of CDW transition (Td=200K) in dehydrogenized 1TTaS2

The CDW transition (T_d=200K) is absent in dehydrogenized 1TTaS₂. A small amount of hydrogen impurity induces the lock-in transition. A new transition is observed in dehydrogenized 1TTaS₂ at 6K. Hydrogen impurity suppresses this transition.     

A pulsed EPR method to determine distances between paramagnetic centers with strong spectral anisotropy and radicals: The dead-time free RIDME sequence

Methods to determine distances between paramagnetic metal centers and radicals are scarce. This is unfortunate because paramagnetic metal centers are frequent in biological systems and so far have not been employed much as distance markers. Successful pulse sequences that directly target the dipolar interactions cannot be applied to paramagnetic metal centers with fast relaxation rates and large g-anisotropy, if no echos can be detected and the excitation bandwidth is not sufficient to cover a sufficiently large part of the spectrum. The RIDME method Kulik et al. (2002) [20] circumvents this problem by making use of the T₁-induced spin-flip of the transition-metal ion. Designed to measure distance between such a fast relaxing metal center and a radical, it suffers from a dead time problem. We show that this is severe because the anisotropy of the metal center broadens the dipolar curves, which therefore, only can be analyzed if the full curve is known. Here, we introduce five-pulse RIDME (5p-RIDME) that is intrinsically dead-time free. Proper functioning of the sequence is demonstrated on a nitroxide biradical. The distance between a low-spin Fe(III) center and a spin label in spin-labeled cytochrome f shows the complete dipolar trace of a transition-metal ion center and a spin label, yielding the distance expected from the structure.     

Time-resolved EPR studies on magnetic interactions between excited triplet (tetraphenylporphinato) zinc and doublet nitroxide radical

By time-resolved electron paramagnetic resonance (TREPR), four (tetraphenylporphinato) zinc (ZnTPP) complexes coordinated by an axial ligand containing a nitroxide radical (NRX; X=4, 5, 8, and 10, denotes the bond number from zinc to nitroxide nitrogen) have been studied in terms of magnetic interactions between the photoexcited triplet state of ZnTPP and NRX. The TREPR spectrum of ZnTPP coordinated by NR10 is almost the same as the one of ZnTPP coordinated by pyridine, indicating that the electron exchange interaction,J, between ZnTPP and the doublet nitroxide is negligibly small. On the other hand, TREPR spectra of the NR4 and NR5 complexes are assigned to the Q₁ state constituted by the ZnTPP and the nitroxide radical. In the case of the ZnTPP-NR8 complex, both T₁ and Q₁ TREPR signals are seen, which may originate from two conformations or degenerate T₁ states of ZnTPP. This EPR study is useful for understanding the photophysical and photochemical properties of chromophores.     

Superconductor-insulator transition in (PbzSn1−z )0.84In0.16Te

The superconductor-insulator transition that occurs at liquid helium temperatures in the (Pb_zSn_1?z )_0.84In_0.16Te semiconductor system with varying lead concentration z = 0.5–0.9 is experimentally investigated. The transition is attributed to the change in the energy characteristics of In impurity centers due to the variation in the amount of lead. The insulator state appears with the transition from the mixed band-impurity conduction, which is characterized by resonant scattering of carriers into the quasilocal indium impurity states, to the hopping conduction between indium impurity states. The sample with z = 0.8 is found to exhibit a variable range hopping conduction described by Mott’s law. Factors that lead to the hopping conduction via impurity states are considered.     

Correlation between local vibrations and metal mass in AlB2‐type transition‐metal diborides

Lattice vibrations have been investigated in TiB₂, ZrB₂ and HfB₂ by temperature‐dependent extended X‐ray absorption fine structure (EXAFS) experiments. Data clearly show that the EXAFS oscillations are characterized by an anomalous behavior of the Debye–Waller factor of the transition‐metal–boron pair, which is suggested to be associated with a superposition of an optical mode corresponding to phonon vibrations induced by the B sublattice and an acoustic mode corresponding to the transition‐metal (TM) sublattice. Data can be interpreted as a decoupling of the metal and boron vibrations observed in these transition‐metal diborides (TMB₂), a mechanism that may be responsible for the significant reduction of the superconducting transition temperature observed in these systems with respect to the parent MgB₂ compound. The vibrational behavior of TM–TM bonds has also been investigated to study the occurrence of anisotropy and anomalies in the lattice vibrational behavior of TM–TM bonds.     

Surface states and its influence on luminescence in ZnS nanocrystallite

In this pape,r the influence of surface effects on the self-activated (SA) luminescence in ZnS nanoparticles prepared by the wet-chemical method is presented. It is observed that the luminescence of SA decreases dramatically by rinsing with methanol. In the rinsed sample, the luminescence of SA increases more by ultraviolet (UV) light irradiation. To clarify its origin, the Raman spectra and electron paramagnetic resonance (EPR) are studied. The results demonstrate that the vibrational modes assigned to organic functional groups of -OH and -COO and -CH₃ decreases remarkably by rinsing, while the EPR signal originated from the unpaired electrons of some transition metal impurity ions including Mn²⁺ increases. It is suggested that the SA centers prefer to occupy the sites near the surface and that the donor of SA emission may be partly related to the organic functional groups of -OH and -COO adsorbed on the surface. The surface-dangling bonds caused by unpaired electrons of some transition metal impurity ions play a role of surface states, leading to the quenching of the SA emissions. The organic functional groups chemically combine with these surface-dangling bonds leading to the decrease in surface states and surface nonradiative relaxation channels and to the increase in the SA emissions.     

低补偿度n-Hg1-xCdxTe的磁致金属-绝缘体相变和相变后的温度激活输运行为

报道了ｘ＝０．２１４组份、低补偿度（Ｋ《１）ｎ－Ｈｇ_1-xＣｄ_xＴｅ晶体在０．３─３０Ｋ温度范围，０─７Ｔ强磁场下的横向磁阻、电子霍耳迁移率、霍耳系数测量结果，观测到了磁致金属－绝缘体相变和相变后的温度激活输运行为。分析实验数据，提出：低补偿度、组份：ｘ＝０．２附近的ｎ－Ｈｇ_1-xＣｄ_xＴｅ，磁致金属－绝缘体相变（ＭＩＴ）发生的机理是载流子在浅施主杂质态上的磁冻结；发生磁冻结的前提是热冻出（ｔｈｅｒｍａｌ ｆｒｅｅｚｅ 关键词：