Dephasing relaxation of the electron spin echo of the vibronic Cu(H(2)O)(6) complexes in Tutton salt crystals at low temperatures.

Two-pulse electron spin echo (ESE) measurements of the phase relaxation (phase memory time T(M)) were performed in a series of Tutton salt crystals M(I)(2)M(II)(SO(4))(2).6X(2)O (M(I)=NH(4), K, Cs; M(II)=Zn, Mg; X=H, D) weakly doped with Cu(2+) ions (c approximately equal to 10(18) ions/cm(3)) in temperature range 4-60 K where ESE signals were detectable. The ESE decay was strongly modulated with proton (or deuteron) frequencies and described by the decay function V(2tau)=V(0)exp(-btau-mtau(2)) with the mtau(2) term being temperature independent and negligible above 20 K. Various mechanisms leading to the tau- or tau(2)-type ESE decay are reviewed. The m and b coefficients for nuclear spectral diffusion (NSD), electron spectral diffusion (SD), and instantaneous diffusion (ID) were calculated in terms of existing theories and the resulting rigid lattice T(0)(M) times were found to be close one to another within the crystal family with average values: 17.5 micros (NSD protons), 200 micros (NSD deuterons), 8 micros (SD), and 5 micros (ID). The ID dominates but the calculated effective T(M)(0) is longer than the experimental T(M)(0)=2 micros. This is due to a nonuniform distribution of the Cu(2+) ions with a various degree of the disorder in the studied crystals. The acceleration of the dephasing rate 1/T(M) with temperature is due to the mechanisms producing exp(-btau) decay. They are reviewed and two of them were found to be operative in Tutton salt crystals: (a) Excitations to the vibronic levels of energy Delta leading to the temperature dependence 1/T(M)=B exp(-Delta/kT), with the vibronic levels produced by strong Jahn-Teller effect, and (b) spin-lattice relaxation processes being effective above 50 K. Based on the Delta values being on the order of 100 cm(-1), the scheme of vibronic levels in the Tutton salts is presented, and the independence of the Delta on temperature proves that the adiabatic potential surface shape of Jahn-Teller active Cu(H(2)O)(6) complexes is not affected by temperature below 65 K.     

Effects of lattice and local dynamics in EPR spectra and electron spin relaxation of vibronic Cu(imidazole)6 complexes in Zn(imidazole)6Cl2·4H2O crystals

Cu(im)₆ complexes in Zn(im)₆Cl₂·4H₂O exhibit a strong Jahn-Teller effect which is static below 100 K and the complex in localized in the two low-energy potential wells. We have reinvestigated electron paramagnetic resonance (EPR) spectra in the temperature range 4.2-300 K and determined the deformation directions produced by the Jahn-Teller effect, energy difference 11 cm⁻¹ between the wells and energy 300 cm⁻¹ of the third potential well. The electron spin relaxation was measured by electron spin echo (ESE) method in the temperature range of 4.2-45 K for single crystal and powder samples. The spin-lattice relaxation is dominated by a local mode of vibration with energy 11 cm⁻¹ at low temperatures. We suppose that this mode is due to reorientations (jumps) of the Cu(im)₆ complex between the two lowest energy potential wells. At intermediate temperatures (15-35 K), the T₁ relaxation is determined by the two-phonon Raman processes in acoustic phonon spectrum with Debye temperature Θ_D=167 K, whereas at higher temperatures the relaxation is governed by the optical phonon of energy 266 cm⁻¹. The ESE dephasing is produced by an instantaneous diffusion below 15 K with the temperature-independent phase memory time , then it grows exponentially with temperature with an activation energy of 97 cm⁻¹. This is the energy of the first excited vibronic level. The thermal population of this level leads to a transition from anisotropic to isotropic EPR spectrum observed around 90 K. FT-ESE gives ESEEM spectrum dominated by quadrupole peaks from non-coordinating ¹⁴N atom of the imidazole rings and the peak from double quantum transition ν_dq. We show that the amplitude of the ν_dq transition can be used to determine the number of non-coordinating nitrogen atoms.     

Origin of the enhanced copper spin echo decay rate in the pseudogap regime of the multilayer high-T(c) cuprates

We report measurements of the anisotropy of the spin echo decay for the inner layer Cu site of the triple layer cuprate Hg(0.8)Re(0.2)Ba(2)Ca(2)Cu(3)O(8) (T(c)=126 K). The angular dependence of the second moment (T(-2)(2M) identical with ) deduced from the decay curves indicates that T(-2)(2M) for H0 parallel c is enhanced in the pseudogap regime below T(pg) approximately 170 K, as seen in bilayer systems. Comparison of T(-2)(2M) between H0 parallel c and H0 perpendicular c indicates that this enhancement is caused by electron spin correlations between the inner and the outer CuO2 layers. The results provide the answer to the long-standing controversy regarding the opposite T dependences of (T1T)(-1) and T(-2)(2G) (T(2G): Gaussian component) in the pseudogap regime of multilayer systems.     

Spin gap in the zigzag spin-1/2 chain cuprate Sr(0.9)Ca(0.1)CuO(2)

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T<90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.     

Antiferromagnetic vortex core in Tl(2)Ba(2)CuO(6+delta) studied by nuclear magnetic resonance

Spatially resolved NMR is used to probe the magnetism in and around vortex cores of nearly optimally doped Tl(2)Ba(2)CuO(6+delta) (T(c)=85 K). The NMR relaxation rate T(-1)1 at the 205Tl site provides direct evidence that the antiferromagnetic (AF) spin correlation is significantly enhanced in the vortex core region. In the core region Cu spins show a local AF ordering with moments parallel to the layers at T(N)=20 K. Above T(N) the core region is in the paramagnetic state which is a reminiscence of the state above the pseudogap temperature (T(*) approximately 120 K), indicating that the pseudogap disappears within cores.     

Quantitative analysis of dinuclear manganese(II) EPR spectra

A quantitative method for the analysis of EPR spectra from dinuclear Mn(II) complexes is presented. The complex [(Me(3)TACN)(2)Mn(II)(2)(mu-OAc)(3)]BPh(4) (1) (Me(3)TACN=N, N('),N(")-trimethyl-1,4,7-triazacyclononane; OAc=acetate(1-); BPh(4)=tetraphenylborate(1-)) was studied with EPR spectroscopy at X- and Q-band frequencies, for both perpendicular and parallel polarizations of the microwave field, and with variable temperature (2-50K). Complex 1 is an antiferromagnetically coupled dimer which shows signals from all excited spin manifolds, S=1 to 5. The spectra were simulated with diagonalization of the full spin Hamiltonian which includes the Zeeman and zero-field splittings of the individual manganese sites within the dimer, the exchange and dipolar coupling between the two manganese sites of the dimer, and the nuclear hyperfine coupling for each manganese ion. All possible transitions for all spin manifolds were simulated, with the intensities determined from the calculated probability of each transition. In addition, the non-uniform broadening of all resonances was quantitatively predicted using a lineshape model based on D- and r-strain. As the temperature is increased from 2K, an 11-line hyperfine pattern characteristic of dinuclear Mn(II) is first observed from the S=3 manifold. D- and r-strain are the dominate broadening effects that determine where the hyperfine pattern will be resolved. A single unique parameter set was found to simulate all spectra arising for all temperatures, microwave frequencies, and microwave modes. The simulations are quantitative, allowing for the first time the determination of species concentrations directly from EPR spectra. Thus, this work describes the first method for the quantitative characterization of EPR spectra of dinuclear manganese centers in model complexes and proteins. The exchange coupling parameter J for complex 1 was determined (J=-1.5+/-0.3 cm(-1); H(ex)=-2JS(1).S(2)) and found to be in agreement with a previous determination from magnetization. The phenomenon of exchange striction was found to be insignificant for 1.     

Nuclear spin resonance of (129)Xe doped with O(2)

Spin-lattice relaxation of (129)Xe nuclei in solid natural xenon has been investigated in detail over a large range of paramagnetic O(2) impurity concentrations. Direct measurements of the ground state magnetic properties of the O(2) are difficult because the ESR (electron spin resonance) lines of O(2) are rather unstructured, but NMR measurements in the liquid helium temperature region (1.4-4 K) are very sensitive to the effective magnetic moments associated with the spin 1 Zeeman levels of the O(2) molecules and to the O(2) magnetic relaxation. From these measurements, the value of the D[Sz(2)-(1/3)S(2)] spin-Hamiltonian term of the triplet spin ground state of O(2) can be determined. The temperature and magnetic field dependence of the measured paramagnetic O(2)-induced excess line width of the (129)Xe NMR signal agree well with the theoretical model with the spin-Hamiltonian D=0.19 meV (2.3 K), and with the reasonable assumption that the E[S(x)(2)-S(y)(2)] spin-Hamiltonian term is close to 0 meV. An anomalous temperature dependence between 1.4 K and 4.2K of the (129)Xe spin-lattice relaxation rate, T(1n)(-1)(T), is also accounted for by our model. Using an independent determination of the true O(2) concentration in the Xe-O(2) solid, the effective spin lattice relaxation time (which will be seen to be transition dependent) of the O(2) at 2.3 K and 0.96 T is determined to be approximately 1.4 x 10(-8)s. The experimental results, taken together with the relaxation model, suggest routes for bringing highly spin-polarized (129)Xe from the low temperature condensed phase to higher temperatures without excessive depolarization.     

Electron spin relaxation of copper(II) ions in diamagnetic crystals

The electron spin-lattice and spin-spin phase relaxation measurements of Cu²⁺ ions in various crystals are reviewed and discussed. Examples of the Debye temperature determination from a wide temperature range measurements of the spin-lattice relaxation time T₁ are shown. An influence of the Jahn-Teller dynamics on T₁ is presented. The phase relaxation described by the phase memory time T_M is affected by temperature due to the spin packet width modulation by molecular motions. The T_M is anisotropic in crystals and can be different for different hyperfine lines of an EPR spectrum.     

Zeeman-driven phase transition within the superconducting state of κ-(BEDT-TTF)2Cu(NCS)2

(13)C nuclear magnetic resonance measurements were performed on κ-(BEDT-TTF)(2)Cu(NCS)(2), with the external field placed parallel to the quasi-2D conducting layers. The absorption spectrum is used to determine the electronic spin polarization M(s) as a function of external field H at a temperature T=0.35 K. A discontinuity in the derivative dM(s)/dH at an applied field of H(s)=213±3 kOe is taken as evidence for a Zeeman-driven transition within the superconducting state and stabilization of inhomogeneous superconductivity.     

Exchange-mediated spin-lattice relaxation of Fe3+ ions in borate glasses

Spin-lattice relaxation times (T1) of two borate glasses doped with different concentrations of Fe2O3 were measured using the Electron Spin-Echo (ESE) technique at X-band (9.630 GHz) in the temperature range 2-6K. In comparison with a previous investigation of Fe3+-doped silicate glasses, the relaxation rates were comparable and differed by no more than a factor of two. The data presented here extend those previously reported for borate glasses in the 10-250K range but measured using the amplitude-modulation technique. The T1 values were found to depend on temperature (T) as T(n) with n approximately 1 for the 1% and 0.1% Fe2O3-doped glass samples. These results are consistent with spin-lattice relaxation as effected by exchange interaction of a Fe3+ spin exchange-coupled to another Fe3+ spin in an amorphous material.     

EPR and HYSCORE investigation of the electronic structure of the model complex Mn(imidazole)6: exploring Mn(II)-imidazole binding using single crystals

The electronic structure of the Mn(II)-imidazole binding was studied by EPR spectroscopy using the model complex Mn(Im)(6) diluted in a single crystal of Zn(Im)(6)Cl(2).4(H(2)O). The second rank zero-field splitting (ZFS) tensor (D tensor) of the two sites, a and b, present in the crystal was determined by measuring the orientation patterns of the echo-detected EPR spectra in three different planes at 10K (D(a)=-106, D(b)=-118, E(a)=-17, E(b)=-22x10(-4)cm(-1). Euler angles with respect to the crystal habitus: alpha(a)=13 degrees , beta(a)=76 degrees , gamma(a)=108.5 degrees , alpha(b)=14 degrees , beta(b)=73.5 degrees , gamma(b)=103.5 degrees ). The contribution of cubic ZFS terms to the spectrum allowed us to determine the orientation of the N-Mn-N directions of the complex as well (Euler angles in the D tensor reference frame alpha=100 degrees , beta=23 degrees , gamma=0 degrees , both centers having the same orientation). The hyperfine interactions with (14)N were explored by HYSCORE spectroscopy. The correlation patterns and modulation amplitudes in the 2D experiments were studied for different electron spin transitions and orientations of the crystal. Signals of three different pairs of nitrogens were found. The results were analyzed considering that the N-Mn binding directions are principal directions of the hyperfine and nuclear quadrupole tensor of (14)N. All three pairs of nitrogens were found to be almost equivalent with an isotropic contribution of A(iso) approximately 3.2MHz and an almost axial anisotropic coupling of 2T approximately 1.1MHz along the N-Mn bonding direction. The nuclear quadrupole principal values are 1.5MHz along the bonding direction, -0.6MHz in the direction perpendicular to the imidazole plane, and -0.9MHz in the direction perpendicular to both.     

Low-frequency spin fluctuations in Skyrmions confined by wires: measurements of local nuclear spin relaxation

We investigate low-frequency electron spin dynamics in a quantum Hall system with wire confinement by nuclear spin relaxation measurements. We developed a technique to measure the local nuclear spin relaxation rate T(1)(-1). T(1)(-1) is enhanced on both sides of the local filling factor ν(wire)=1, reflecting low-frequency fluctuations of electron spins associated with Skyrmions inside the wire. As the wire width is decreased, the fast nuclear spin relaxation is suppressed in a certain range of Skyrmion density. This suggests that the multi-Skyrmion state is modified and the low-frequency spin fluctuations are suppressed by the wire confinement.     

Uniform mixing of antiferromagnetism and high-temperature superconductivity in electron-doped layers of four-layered Ba(2)Ca(3)Cu(4)O(8)F(2): a new phenomenon in an electron underdoped regime

We report (63,65)Cu- and (19)F-NMR studies on a four-layered high-temperature superconductor Ba(2)Ca(3)Cu(4)O(8)F(2)((0234F(2.0)) with apical fluorine (F(-1)), an undoped 55 K superconductor with a nominal Cu(2+) valence on average. We reveal that this compound exhibits the antiferromagnetism (AFM) with a Néel temperature T(N)=100 K despite being a T(c)=55 K superconductor. Through a comparison with a related trilayered cuprate Ba(2)Ca(3)Cu(4)O(8)F(2)(0233F(2.0)), it is demonstrated that electrons are transferred from the inner plane (IP) to the outer plane (OP) in 0234F(2.0) and 0223F(2.0), confirming the self-doped high-temperature superconductivity (HTSC) having electron and hole doping in a single compound. Remarkably, uniform mixing of AFM and HTSC takes place in both the electron-doped OPs and the hole-doped IPs in 0234F(2.0).     

Electron spin-relaxation via vibronic level of nickel (I) and nickel (III) cyanide complexes in NaCl single crystals

Electron spin-lattice relaxation rates for the low spin [Ni(CN)(4)](1-) and [Ni(CN)(4)](3-) complexes in NaCl host lattice were measured by the inversion recovery technique in the temperature range 7-50K. The data for both paramagnetic species fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g-tensor temperature dependence.     

Proton NMR T 1 Studies in Methylammonium TrichlorO Stannate(II) (CH 3 NH 3 SnCl 3 )

Proton spin lattice relaxation time ( T 1 ) measurements have been carried out in methylammonium trichloro stannate(II) (CH 3 NH 3 SnCl 3 ) as a function of temperature in the range 317-5 K at a Larmor frequency of 10 MHz. The temperature dependence of T 1 shows a phase transition around 220 K and four T 1 minima (294 K, 62 K, 32 K and 12 K). The results are discussed in terms of proton dynamics, namely, uncorrelated reorientation of NH 3 and CH 3 groups at high temperatures and tunnelling of NH 3 and CH 3 protons at low temperatures.     

Direct evidence for a dynamical ground state in the highly frustrated Tb(2)Sn(2)O(7) pyrochlore

mSR experiments have been performed on a powder sample of the "ordered spin ice" Tb(2)Sn(2)O(7) pyrochlore. At base temperature (T=35 mK), the muon relaxation is found to be of dynamical nature, which demonstrates that strong fluctuations persist below the ferromagnetic transition (T(C)=0.87 K). Hints of long-range ordering appear as oscillations of the muon polarization when an external field is applied and also as a hysteretic behavior below T(C). We propose that dynamics results from fluctuations of clusters of correlated spins with the ordered spin ice structure.     

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.     

Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR,optical and magnetic susceptibility measurements

Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(II) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120K static Jahn-Teller distortion sets in and below 110 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K. From an optical study the Jahn-Teller stabilization energy is found to be ～2250cm^?1. Comparison of Abs_max values for other silver(II) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5–40 K with 2J = 0.906cm^?1, and above 40K it is ferromagnetically coupled with 2J = +7.4cm^?1. The effective magnetic moment (μ_eff) of this complex has been compared with that of a series of other silver(II) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(II) complex.     

Metamagnetic quantum criticality revealed by 17O-NMR in the itinerant metamagnet Sr3Ru2O7

We have investigated the spin dynamics using 17O-NMR in the bilayered perovskite Sr3Ru2O7, which sits close to a metamagnetic quantum critical point. The nuclear spin-lattice relaxation rate divided by temperature 1/T1T is enhanced on approaching the metamagnetic critical field of approximately 7.9 T, and at the critical field 1/T1T continues to increase and does not show Fermi-liquid behavior down to 0.3 K. The temperature dependence of T1T in this region suggests the critical temperature Theta to be approximately 0 K, which is strong evidence that the spin dynamics possesses a quantum critical character. Comparison between uniform susceptibility and 1/T1T reveals that antiferromagnetic fluctuations instead of two-dimensional ferromagnetic fluctuations dominate the spin fluctuation spectrum at the critical field, which is unexpected for itinerant metamagnetism.     

Effect of molecular motion on electron spin phase memory times for copper(II) complexes in doped solids

Electron spin phase memory times,T _m, as a function of temperature were measured for Cu(II) bis(diethyldithiocarbamate), Cu(Et₂dtc)₂; Cu(II) bis(diethyldithiophosphate), Cu(Et₂dtp)₂; Cu(II) bis(diphenyldithiophosphate), Cu(Ph₂dtp)₂; Cu(II) tetratolylporphyrin, CuTTP; vanadyl 5-(4-carboxyphenyl)-10,15,20-tritolylporphyrin, VOTTP-COOH; and Ag(II) tetratolylporphyrin, AgTTP, doped into powdered samples of closely-related diamagnetic hosts. For the three metalloporphyrins, the electron spin relaxation rate (1/T _m) increased monotonically with increasing temperature. However the temperature dependence of the relaxation rate was not monotonic for the three other Cu(II) complexes. For Cu(Et₂dtc)₂ and Cu(Et₂dtp)₂ the temperature dependence of 1/T _m between about 85 and 130 K is attributed to the effects of methyl rotation, with activation energies of 1.0 kcal/mole. Between 120 and 250 K the 1/T _m data for Cu(Ph₂dtp)₂ exhibit effects that are attributed to motion of the phenyl rings.