Intercalation reactions of ruthenium-(III)-chloride via electron/ion transfer

The layered anisotropic semiconductor α-RuCl₃ is able to undergo a wide variety of intercalation reactions via electron/ ion transfer and subsequent exchange reactions. The structures of hydrated phases (Aⁿ⁺)_x/n(H₂O)_y [RuCl₃]^x- wit h alkali, alkaline earth and transition metal ions are related to the hydration enthalpies of the guest cations. The hydrated phases are polyelectrolytes and show cooperative ion exchange phenomena. Cathodic reduction of α-RuCl₃ in concentrated aqueous mineral acids yields the hydrogen bronze H_xRuCl₃ while from dilute acids hydronium phases (H₃O⁺)_x(H₂O)_y[RuCl ₃]^x- are obtained whose hydrate structures are dependent upon the acid concentration. Among the cations which intercalate as unsolvated species (Cu⁺, Ag⁺, Tl⁺) the copper phases exhibit different reaction mechanisms in aqueous and aprotic electrolytes. A comparison of the topotactic reactivity of α-RuCl₃ and of layered transition metal dichalcogenides MX₂ reveals a remarkable similarity.     

Magnetic field effect on electron transfer reactions of flavin derivatives associated with micelles

The magnetic field effects (MFEs) on the electron transfer reactions from indole derivatives to flavin derivatives in micellar solutions are studied. The MFEs on the free radical yields observed by transient absorption (TA) reflect effectively the association of the donor and acceptor molecules with the micelles. In the system of riboflavin and indole, the MFE increases rapidly with increasing concentration of sodium dodecyl sulfate (SDS) higher than the critical micellar concentration. In contrast, in the system of flavin mononucleotide and indole, the increase of MFE is very slow even at higher concentrations of SDS. This result shows that riboflavin is well associated with the SDS micelle and the diffusion process of the radical pair is restricted by the micellar cages. The MFE in the system of riboflavin and indole is twice as large as that of riboflavin and tryptophan. This result shows the difference of the dynamics of radicals in micelles. The escape rate of the cation radical generated from tryptophan is much faster than that generated from indole. The dependence of the MFEs on the type of surfactant is studied. The effect of the Coulomb force between the ionic reactant molecules and the charged head group of the surfactant and the effect of the molecular size are discussed by comparison of the MFE intensities.     

Coherent manipulation of electron spins up to ambient temperatures in Cr5+ (S = 1/2) doped K3NbO8

We report coherent spin manipulation on Cr(5+) (S = 1/2, I = 0) doped K(3)NbO(8), which constitutes a dilute two-level model relevant for use as a spin qubit. Rabi oscillations are observed for the first time in a spin system based on transition metal oxides up to room temperature. At liquid helium temperature the phase coherence relaxation time T2 reaches approximately 10 micros and, with a Rabi frequency of 20 MHz, yields a single-qubit figure of merit Q(M) of about 500. This shows that a diluted ensemble of Cr(5+) (S = 1/2) doped K(3)NbO(8) is a potential candidate for solid-state quantum information processing.     

Magnetic properties of a 3d nanoparticle (S=5/2) studied with a quantum simulation model

A quantum simulation model was developed and employed in this work to study the magnetism of an assumed 3d nanoparticle, which consists of an antiferromagnetic core and a ferromagnetic shell. The calculated magnetic structures, specific heat, magnetization and hysteresis curves are reasonable physically, demonstrating the correctness of the quantum model and the applicability of the simulation algorithm.     

Longitudinal Susceptibility of S = 1/2 Low-Dimensional Heisenberg Ferromagnet in a Magnetic Field

Longitudinal susceptibility of the spin-1/2 low-dimensional Heisenberg ferromagnet in a magnetic field, is studied by the Green's function method within the random phase approximation. The static and dynamic longitudinal susceptibilities are calculated in the low- and high-field regions. Power laws for the position and height of the static susceptibility maximum are shown not to support the predictions of Landau theory.     

Heat capacity of a five-coordinated iron(III) complex with spin S = 32, bromobis(N,N-diethyldithiocarbamato)iron(III), between 0.4 and 300 K

Heat capacity measurements have been made for six kinds of specimens prepared by different methods. Among them, Sample A exhibited a A-type ferromagnetic pahse transition at 1.347 K and a Schottky-type anomaly due to the zero-field splitting around 9K. The total entropy and enthalpy were (11.05 ± 0.04) J K^?1mol^?1 and (97.0 ± 0.4) J mol^?1, respectively. Sample B exhibited a Sehottky-type anomaly around 0.4 K due to the ferro-magnetic dimeric coupling with $\text{J}{}_{\mathrm{D}}\text{k}\text{= + 0.30}\text{K}$ as well as the Schottky-type anomaly at 9K. The total magnetic entropy and enthalpy were (11.45 ± 0.03) JK^?1 mol^?1 and (93.8 ± 0.8) J mol^?1, respectively. The remaining samples are simple mixtures of the λ-type modification and the dimeric modification. Irrespective of the magnetic behavior at low temperatures, all the samples showed a non-magnetic first-order phase transition around 270 K. The heat capacity and entropy of this phase transition have been accounted for in terms of the Frenkel theory of heterophase fluctuation. Construction of an adiabatic-type calorimeter workable between 1.5 and 393 K has been also presented.     

Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)₂(4AMP)(DA)](ClO₄)₃ and cis-[Co(dmp)₂(C₁₂H₂₅NH₂)₂](ClO₄)₃ (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C₁₂H₂₅NH₂ = dodecylamine) by Fe²⁺ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS^# and ΔH^#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.     

Specific heat study of an S = 1/2 alternating Heisenberg chain system: F5PNN in a magnetic field

We have measured the specific heat of an S = 1/2 antiferromagnetic alternating Heisenberg chain pentafulorophenyl nitronyl nitroxide in magnetic fields up to H > H(C2). This compound has a field-induced magnetic ordered (FIMO) phase between H(C1) and H(C2). Characteristic behaviors are observed depending on the magnetic field up to above H(C2) outside of the H-T boundary for the FIMO. The temperature and field dependence of the specific heat are qualitatively in good agreement with the theoretical calculation on an S = 1/2 two-leg ladder [Wang et al., Phys. Rev. Lett. 84, 5399 (2000)]]. This agreement suggests that the observed behaviors are related with the low-energy excitation in the Tomonaga-Luttinger liquid.     

Magnetic properties of RCoSi2 compounds (R=rare earth)

New ternary silicides of composition RCoSi₂ (R=rare earth and Y) have been prepared and found to crystallize in the orthorhombic CeNiSi₂-type structure. Their magnetic properties have been studied by means of susceptibility measurements between 2 and 250 K. The Ce and Y compounds show essentially temperature independent Pauli paramagnetism. The compounds with R=Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm show antiferromagnetic ordering below 20 K. The effective rare earh moments in the paramagnetic state agree well with the free ion values, and, for the heavy rare earths, the Néel temperatures vary with the De Gennes factor. There is no indication for a magnetic contribution from the Co sublattice.     

Intramolecular electron transfer in mixed-valence complexes [(NH3)5Ru-L-Ru(NH3)5]5+ (L = N2, pyz, pym, 4,4’-bipy, bpa)

The dynamics of the intramolecular electron transfer from Ru(II) to Ru(III) in binuclear mixed-valence complexes [NH₃)₅Ru -L-Ru(NH₃)₅]⁵⁺ (L = N₂, pyz, bipy, pym, bpa) is analyzed by the semiempirical CINDO + CI method. Translated from ZhurnalStruktumoi Khimii, Vol. 39, No. 4, pp. 579–590, July–August, 1998.     

5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

通过水解TiCl₄制备了锐钛矿结构TiO₂纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO₂纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO₂纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D^*)与电荷分离态波函数Ψ(D⁺ +e^-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO₂纳米粒子体系时, 电子以两种不同方式注入TiO₂纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO₂)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ₁=41 ps (74.4%) 和τ₂=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO₂纳米粒子体系的荧光分别以时间常数为τ₁=44 ps (90.4%), τ₂=478 ps (8.6%) 和τ₃=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.     

N=6 Supergravity on Ad S5 and the SU(2,2/3) Superconformal Correspondence

It is argued that N=6 supergravity on Ad S5, with the gauge group SU(3)× U(1) corresponds, at the classical level, to a subsector of the chiral primary operators of N=4 Yang–Mills theories. This projection involves a duality transformation of N=4 Yang–Mills theory and therefore can be valid if the coupling is at a self-dual point, or for those amplitudes that do not depend on the coupling constant.     

EPR powder spectra of Co(II) and Cr(III) in MgIn2S4 spinel

The EPR powder spectra of high spin Co(II) and Cr(III) diluted in partially inverse spinel matrix MgIn₂S₄ are reported. While the spectrum of Co(II) in octahedral sites is orthorhombic the Cr(III) one is axial. Evidence is given that the EPR spectra cannot be directly associated with the cation distribution of the matrix.     

Comparative analysis of crystal field effects and energy level scheme of six-fold coordinated Cr ion in the pyrochlores, Y2B2O7 (B=Ti, Sn)

The electronic energy levels of the six-fold coordinated Cr⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B=Sn⁴⁺, Ti⁴⁺), have been computed using the exchange charge model of crystal field theory. The calculated Cr⁴⁺ energy levels and their trigonal splitting are in good agreement with experimental spectra. Calculations of the crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ (in comparison with Y₂Ti₂O₇) arises from increased orbital overlap effects between the Cr⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. The increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Cr⁴⁺-O^2- bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇. This is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. As a result, a stronger crystal field is experienced by Cr⁴⁺ ions in Y₂Sn₂O₇, even if the Cr⁴⁺-O²⁻ distances are greater in this case, when compared to those in Y₂Ti₂O₇.     

Electron paramagnetic resonance linewidth in a two-dimensional Heisenberg antiferromagnet (S=1/2) with skyrmeons

Electron magnetic relaxation was studied in a two-dimensional Heisenberg antiferromagnet (S=1/2) with skyrmeons. The electron paramagnetic resonance (EPR) linewidth (Г_⊥) was calculated at temperatures T≤J (J is the nearest-neighbor interaction constant). The magnitude of Г_⊥ caused by the Dzyaloshinskii-Moriya interaction is shown to grow as r ₀/a with decreasing temperature, whereas the anisotropic symmetric interaction leads to the (r ₀/a)³ dependence, where r ₀ is the average size of a skyrmeon and a is the lattice parameter. The results obtained agree qualitatively with calculations performed on the basis of a renormalization-group (RG) analysis of the nonlinear σ model at .     

Energy, fine structure, and hyperfine structure of the core-excited states 1s2s2pnp 5P (n = 2–5) and 1s2p2mp 5S (m = 2–5) for Li- ion

The relativistic energies, the oscillator strength, and the lifetimes of high-lying core-excited states 1s2s2pnp ⁵P (n=2–5) and 1s2p²mp ⁵S^o (m=2–5) of Li^- ion are calculated with the saddle-point variational method and restricted variation method. The fine structure and the hyperfine structure of the core-excited states for this system are also explored. The results are compared with other theoretical and experimental data in the literature.     

Mn5Ge2.7M0.3 (M=Ga，Al，Sn) 化合物的磁性和磁熵变

研究了Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物的磁性和磁熵变. x射线衍射实验表明，研究的化合物均呈六角Mn₅Si₃型结构. 三种原子对Ge原子的替代，使得平均Mn原子磁矩下降，但居里温度没有明显的变化. 由于磁矩的降低，导致磁熵变值的下降，在磁场变化为4.0×10⁶A·m^-1时，对应于M=Ga，Al和Sn的样品，最大磁熵变值ΔS^max_Ｍ分别为6.1，6.3和5.3J·kg^-1K^-1，但磁熵变峰值的半高宽ΔＴ_ＦＷＨＭ有所增加. 另外，Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物在高于居里温度的Arrott曲线上出现了一个不连续点，即样品在一定温度下的顺磁磁化率在某一临界磁场下发生了突变，临界磁场与温度几乎呈正比关系.这可能是由于样品在加一定磁场时3d带的费米能级发生了变化，使得有效电子数的减少所致. 关键词： 居里温度 平均Mn原子磁矩 磁熵变 Arrott图     

Magnetic and structural investigations on substituted Pr2Co17-xTx systems (T= Fe, Mn, Cr, Cu and Al)

Magnetic and structural characteristics of Pr₂Co₁₇-based ternaries, in which Co is partly replaced by other transition elements, namely Fe, Mn, Cr, Cu and Al, have been investigated. The objective of the work was to explore the possibility of enhancing the anisotropy of Pr₂Co₁₇ to the point that it would be useful for permanent magnet fabrication. X-ray diffraction indicates that all the systems studied occur in the rhombohedral Th₂Zn₁₇ structure. The cell constants increase as Fe, Mn, etc., are introduced in the system, which indicates that substitution occurs in the Co sublattice. The Curie temperatures, T_c, decrease monotonically with increasing x in the order Fe < Cu < Mn < Al < Cr. The saturation magnetization, M_s, increases with increasing x for the Fe system with x 8. For x #62; 8 in the Pr₂Co_17-xFe_x system and in all other ternary systems st died, M_s decreases with x, the magnitude of the effect being in the order Cr #62; Al #62; Mn #62; Cu. The rate of decrease is larger than that expected as a simple dilution except for the systems containing Cu. Significant modification of the anisotropy characteristics of Pr₂Co₁₇ is observed upon substitution. The planar anisotropy of Pr₂Co₁₇ becomes uniaxial with Fe (x 4) and Mn (x 2) substitutions. With Cr and Al substitutions, the plane-seeking tendency of Pr₂Co₁₇ is significantly weakened.