Electron spin relaxation in solutions of manganese (II) ions

Measurements of the neutron scattering static structure factor S(Q) are reported for orthobaric liquid fluorine at 77K for an incident wavelength of 1·2Å. The observed S(Q) and the atom-atom correlation function are discussed and compared with those of other halogens and oxygen. From the d(r) pair distribution function it is shown that liquid fluorine has a coordination number of first neighbours more similar to liquid oxygen than halogens. The number of atoms in the first and second coordination shell is in good agreement with a close-packed arrangement of atoms.     

Electron spin relaxation of copper(II) complexes in glassy solution between 10 and 120 K

The temperature dependence, between 10 and 120 K, of electron spin-lattice relaxation at X-band was analyzed for a series of eight pyrrolate-imine complexes and for ten other copper(II) complexes with varying ligands and geometry including copper-containing prion octarepeat domain and S100 type proteins. The geometry of the CuN4 coordination sphere for pyrrolate-imine complexes with R=H, methyl, n-butyl, diphenylmethyl, benzyl, 2-adamantyl, 1-adamantyl, and tert-butyl has been shown to range from planar to pseudo-tetrahedral. The fit to the recovery curves was better for a distribution of values of T1 than for a single time constant. Distributions of relaxation times may be characteristic of Cu(II) in glassy solution. Long-pulse saturation recovery and inversion recovery measurements were performed. The temperature dependence of spin-lattice relaxation rates was analyzed in terms of contributions from the direct process, the Raman process, and local modes. It was necessary to include more than one process to fit the experimental data. There was a small contribution from the direct process at low temperature. The Raman process was the dominant contribution to relaxation between about 20 and 60 K. Debye temperatures were between 80 and 120 K. For samples with similar Debye temperatures the coefficient of the Raman process tended to increase as gz increased, as expected if modulation of spin-orbit coupling is a major factor in relaxation rates. Above about 60 K local modes with energies in the range of 260-360 K (180-250 cm-1) dominated the relaxation. For molecules with similar geometry, relaxation rates were faster for more flexible molecules than for more rigid ones. Relaxation rates for the copper protein samples were similar to rates for small molecules with comparable coordination spheres. At each temperature studied the range of relaxation rates was less than an order of magnitude. The spread was smaller between 20 and 60 K where the Raman process dominates, than at higher temperatures where local modes dominate the relaxation. Spin echo dephasing time constants, Tm, were calculated from two-pulse spin echo decays. Near 10 K Tm was dominated by proton spins in the surroundings. As temperature was increased motion and spin-lattice relaxation made increasing contributions to Tm. Near 100 K spin-lattice relaxation dominated Tm.     

Electron paramagnetic relaxation in aqueous solutions of manganese (II) ions

The processes of the electron paramagnetic relaxation, molecular motions and structural changes in aqueous solutions of manganese nitrate have been investigated by direct measurement of spin-lattice (T ₁) and spin-spin (T ₂) relaxation times for a wide range of concentrations, temperatures and viscosities. T ₁ and T ₂ were measured by a non-resonance absorption method.

It was discovered that some structural regions exist at the different concentrations of Mn(II) ions in solution. So, the structure of highly concentrated solutions may be considered as one of the corresponding crystallohydrate. The structural microinhomogeneities were observed also in the intermediate concentration range at definite temperatures. It is shown that the relaxation mechanism proposed by Bloembergen and Morgan is not effective in the concentration range studied by us.

The analysis of relaxation times and E.P.R. spectra has shown the formation of ‘liquid microphases’ at the freezing point of the solution. Such microphases can exist at temperatures a few tenths of a degree below the solvent freezing point, and its composition considerably differs from the initial solution.

The correlation times for intramolecular and intermolecular electron relaxation mechanisms are evaluated and their nature is discussed.     

Electron spin relaxation in pseudo-Jahn-Teller low-symmetry Cu(II) complexes in diaqua(L-aspartate)Zn(II).H(2)O crystals.

Low-temperature (4-55 K) pulsed EPR measurements were performed with the magnetic field directed along the z-axis of the g-factor of the low-symmetry octahedral complex [(63)Cu(L-aspartate)(2)(H2O)2] undergoing dynamic Jahn-Teller effect in diaqua(L-aspartate)Zn(II) hydrate single crystals. Spin-lattice relaxation time T(1) and phase memory time T(M) were determined by the electron spin echo (ESE) method. The relaxation rate 1/T(1) increases strongly over 5 decades in the temperature range 4-55 K. Various processes and mechanisms of T(1)-relaxation are discussed, and it is shown that the relaxation is governed mainly by Raman relaxation processes with the Debye temperature Theta(D)=204 K, with a detectable contribution from disorder in the doped Cu(2+) ions system below 12 K. An analytical approximation of the transport integral I(8) is given in temperature range T=0.025-10Theta(D) and applied for computer fitting procedures. Since the Jahn-Teller distorted configurations differ strongly in energy (delta(12)=240 cm(-1)), there is no influence of the classical vibronic dynamics mechanism on T(1). Dephasing of the ESE (phase relaxation) is governed by instantaneous diffusion and spectral diffusion below 20 K with resulting rigid lattice value 1/T(0)(M)=1.88 MHz. Above this temperature the relaxation rate 1/T(M) increases upon heating due to two mechanisms. The first is the phonon-controlled excitation to the first excited vibronic level of energy Delta=243 cm(-1), with subsequent tunneling to the neighbor potential well. This vibronic-type dynamics also produces a temperature-dependent broadening of lines in the ESEEM spectra. The second mechanism is produced by the spin-lattice relaxation. The increase in T(M) is described in terms of the spin packets forming inhomogeneously broadened EPR lines.     

Spin-spin relaxation in heteropolynuclear clusters containing iron(III) and copper(II) ions

The magnetic coupling between Fe(III) and Cu(II) and the relaxation behavior of the spin centered at the iron have been studied in di- and trinuclear clusters. The experimental spectra have been analyzed in terms of a simple cross-relaxation model. In the strongly coupled trimer the relaxation rates are determined by a Boltzmann factor and a single field- and temperature-independent scaling parameter¹ w ₀, while the weakly coupled dimer exhibits obviously a more complex behavior.     

Electron spin resonance in manganese-doped BSCCO (2212) crystals

The electron spin resonance (ESR) spectra of undoped and manganese-doped BSCCO (2212) crystals (nominal composition Bi₂Sr₂CaCu_2–x Mn_xO_y, where x=0.1) are compared. Zh. Tekh. Fiz. 67, 137–138 (October 1997)     

Electron spin relaxation via vibronic level of rhodium(II) hexacyanide complex in KCl crystal

Electron spin-lattice relaxation rates for the low-spin [Rh(CN)(6)](4-) complex in KCl were measured by the inversion recovery and saturation recovery techniques, in the range of 5 to 30 K. Angular variation experiments indicate that electron spin-lattice relaxation times present axial symmetry. The data fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g tensor temperature dependence.     

Electron spin relaxation studies of impurity iron ions in ferroelectric lithium niobate

The nuclear hyperfine structure of dilute impurity iron ions in ferroelectric lithium niobate is investigated via⁵⁷Fe Mössbauer effect (ME). The ME spectra exhibit typical slow electron spin relaxation effects associated with Fe³⁺ ions in the⁶S_5/2 state, which are analysed using spin-Hamiltonian formalism. For Fe³⁺ ions, the principal axis of EFG tensor is found to be parallel to the crystallographic c-axis. The strong external magnetic field of 47 KOe is used to study magnetic and crystal field effects on the ME hyperfine structure.     

Electron spin resonance of copper pair centers in crystals with perovskite structure

Copper pair centers, which could be of interest for obtaining quantitative information about exchange interactions in superconductors based on cuprate perovskites, are observed in crystals with the perovskite structure by the ESR method. Such centers are investigated in KTaO₃:Cu and K_1−x Li_xTaO₃:Cu crystals. A model consisting of a chain of two equivalent Cu²⁺ ions and three oxygen vacancies, extending along the 〈 100〉 axis, is proposed for the centers. The exchange interaction in the pairs is ferromagnetic. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 12, 890–894 (25 June 1999)     

Electron spin relaxation of gadolinium (III) complexes in dimethylformamide solution

The characteristics of spontaneous Raman scattering from solutions of diatomic molecules are reviewed, especially with regard to what they may tell one about the dynamics of molecular motion. In the limit of extreme motional narrowing the polarized component of the Q branch is a lrentzian with a width which depends upon the rate (τ^-1) of dephasing of the molecular vibrations. An approximate, closed, quantum-mechanical expression for the contribution of ‘translational-translational’ quasielastic scattering to τ^-1, called τ_ph ^-1(T-T), is derived. The translational states of the liquid are determined by invoking the Lennard-Jones-Devonshire (LJD) cell model. The full LJD cell potential is replaced by an harmonic approximation thereto. The dependence of the τ_ph(T-T) upon thermodynamic variables and microscopic properties is discussed. The derived expression for τ_ph ^-1 (T-T) is then used to compute upper bounds on τ for liquid N₂ and O₂, for which experimental data are available. It is concluded that the T-T quasielastic scattering mechanism is essentially negligible and that other mechanisms must be dominant in determining τ. In particular, it is suggested that solvent-induced vibrational-reorientational coupling may be quite important.     

Electron exchanges in nuclear spin conversion of hydrogen physisorbed on diamagnetic insulators

Models are provided and discussed to interpret new experiments on the ortho-paraconversion of hydrogen “physisorbed” on dielectric and diamagnetic surfaces.Electro-static and dynamical molecule-surface interactions complemented by hyperfinecontacts are shown to be generally more effective than the magnetic ones. Coulombrepulsion induces exchanges of molecular and surface electrons and excites triplet spinstates which are effective in the angular momenta transfers to the catalyst. Theconversion time is obtained as the square of a ratio of two energies: the exchange andexcitation ones. The main channel is found composed of triplet excitations of the order ofthe eV, induced by molecule-surface exchanges of about a hundred of meV. It explains thezinc and oxygen rates of about one minute observed on the MOF samples as well as the aboutten times slower ones on the ASW. The same mechanism is also shown to occur in thetransient regime, but faster. Finally it explains also the conversion of a few hoursobserved for interstitial hydrogen in silicium by transitions to the conduction bandinduced by about 10 meVelectron exchanges. The molecule-surface orbital geometries of the MOF and ASWconfigurations are displayed and the quantum path when unfolded exhibits the successivebroken symmetries.     

半导体量子阱中电子自旋弛豫和动量弛豫

根据电子自旋轨道耦合对自旋极化弛豫影响的DP机理进一步导出了半导体中电子自旋弛豫与动量弛豫及载流子浓度的关系，并采用飞秒抽运探测技术在室温下测量AlGaAs/GaAs 多量子阱中载流子浓度在 1×10¹⁷—1×10¹⁸cm^-3范围内，电子自旋弛豫时间由58ps增加至82 ps的变化情况，与理论计算值符合，说明了随着载流子浓度的增加，载流子间的频繁散射加速了电子动量驰豫，减弱了电子自旋轨道耦合作用，从而延长了电子自旋寿命. 关键词： 电子自旋轨道耦合 电子自旋弛豫和动量弛豫 飞秒光谱技术     

ENDOR and transferred hyperfine interaction of impurity rare-earth ions with nearest diamagnetic ions in crystals

The tetragonal Er³⁺ ion associated with the interstitial F^? ion along the [100] axis in CaF₂ is studied using ENDOR. The parameters of the transferred hyperfine interaction and of the nuclear Zeeman interaction of the surrounding fluorine ions are determined. Anomalously large values of the pseudo-nuclear Zeeman effect on the F^? nuclei are found. The theoretical analysis of these parameters is carried out in a frame of operator techniques in the theory of transferred hyperfine interactions. A number of useful relations for practical calculations of the values of the local field at ligand nuclei are reported.     

Electron spin echo modulation and relaxation in polythiophene

Electron spin echo measurements on neutral poly (thiophene) show a clear modulation of the spin-echo decay. Analysis of the modulation and its Fourier transformed (ω) power spectrum indicates that the wave function of the spin defect is extended over ～ 25 proton nuclei. The functional behavior of the longitudinal relaxation, T₁, versus temperature is very similar to that observed previously for (CH)_x, although T₁ values for poly (thiophene) are significantly longer.     

Electron spin relaxation as a tool for studying the dynamics in the outer solvation sphere of 6S spin state ions

The apparently homogeneous E.S.R. spectra of solution manganous ions are interpreted in terms of a sum of degenerate lorentzian lineshapes with different widths. The existence of a distribution of linewidths instead of a single linewidth, is interpreted assuming that the electron spin relaxation is dominated by rotation of a static zero-field splitting tensor caused by slow configurational changes of the ionic environment, including first and second solvation spheres. Typical configurational lifetimes of the second solvation sphere were found to be τ _k ～ 10^-9 s. Details of the ionic structure and dynamics are discussed.     

Electron spin relaxation of triarylmethyl radicals in fluid solution

Electron spin relaxation times of a Nycomed triarylmethyl radical (sym-trityl) in water, 1:1 water:glycerol, and 1:9 water:glycerol were measured at L-band, S-band, and X-band by pulsed EPR methods. In H(2)O solution, T(1) is 17+/-1 micros at X-band at ambient temperature, is nearly independent of microwave frequency, and exhibits little dependence on viscosity. The temperature dependence of T(1) in 1:1 water:glycerol is characteristic of domination by a Raman process between 20 and 80 K. The increased spin-lattice relaxation rates at higher temperatures, including room temperature, are attributed to a local vibrational mode that modulates spin-orbit coupling. In H(2)O solution, T(2) is 11+/-1 micros at X-band, increasing to 13+/-1 micros at L-band. For more viscous solvent mixtures, T(2) is much shorter than T(1) and weakly frequency dependent, which indicates that incomplete motional averaging of hyperfine anisotropy makes a significant contribution to T(2). In water and 1:1 water:glycerol solutions continuous wave EPR linewidths are not relaxation determined, but become relaxation determined in the higher viscosity 1:9 water:glycerol solutions. The Lorentzian component of the 250-MHz linewidths as a function of viscosity is in good agreement with T(2)-determined contributions to the linewidths at higher frequencies.     

Toxic effects of copper (II) ions on bovine hemoglobin

In this paper, the toxic influence of copper ions (II) on bovine hemoglobin was investigated by the combination of ultraviolet-visible absorption, fluorescence, time-resolved fluorescence, synchronous fluorescence, and circular dichroism spectra. Driven by hydrophobic and electrostatic forces, copper ions (II) could interact with bovine hemoglobin to form bovine hemoglobin-copper ions (II) complex with one binding site. The binding constant (K) was 1.57?×?10⁴, 1.89?×?10⁴ and 2.11?×?10⁴?L/mol at 298, 304, and 310?K, respectively. The binding distance (r) was 4.24?nm. Fluorescence and time-resolved fluorescence spectra showed that bovine hemoglobin quenched by copper ions (II) was a static quenching process. Results of synchronous fluorescence spectra revealed that the microenvironment and the conformation of bovine hemoglobin were changed during the binding reaction. Data of circular dichroism spectra suggested that with the increasing concentration of copper ions (II), the secondary structure of bovine hemoglobin underwent a decrease in α-helix and alteration in backbone microenvironment. Copper ions (II) was thus evidenced to have a certain toxic effect on physical bodies.     

Magnetoplastic effect in LiF crystals and longitudinal spin relaxation

New features of the dependence of the average travel distance l of dislocations on the magnetic field B have been found in an investigation of the magnetostimulated dislocation mobility in LiF crystals: A transition has been found from ordinary proportionality l∝B ² to saturation l≈ const in high fields B. It is shown that the experimental points can be described satisfactorily by the theoretical dependence l∝ [(B ₀/B)²+1]⁻¹ (B ₀≈0.8 T), typical for the mechanism of longitudinal spin relaxation in a system of radical pairs, which are supposedly formed when dislocation nuclei interact with paramagnetic impurity centers. According to the theory, the level of the field B ₀ is determined by the characteristic frequency of the oscillations of the internal fields in the lattice, which for B ₀∼1 T is of the order of 10¹¹s⁻¹, which corresponds to the typical frequency of characteristic oscillations of dislocation segments between pinning centers, which, naturally, does not depend on temperature. This in turn explains the fact that the measured values of B ₀ are the same at 293 K and 77 K. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 11, 749–753 (10 December 1999)     

Electron spin relaxation rates for nitridochromium(V) tetratolylporphyrin and nitridochromium(V) octaethylporphyrin in Frozen solution

T ₁ andT _m for nitridochromium(V) tetratolylporphyrin and nitridochromium(V) octaethylporphyrin were measured by saturation recovery and electron spin echo EPR, respectively, between 10 and 130 K. The temperature dependence of 1/T ₁ was similar to that observed previously for chromium(V) complexes of hydroxycarboxylic acids. The spin lattice relaxation rate was faster in the perpendicular plane (the porphyrin plane) than normal to this plane. 1/T _m was orientation dependent with the fastest rates observed for orientations intermediate between the principal axes. The orientation dependence of 1/T _m increased with increasing temperature and decreasing rigidity of the matrix, and is attributed to molecular motion.