Modulation of the distance dependence of paramagnetic relaxation enhancements by CSA × DSA cross-correlation

Paramagnetic metal ions with fast-relaxing electronic spin and anisotropic susceptibility tensor provide a rich source of structural information that can be derived from pseudo-contact shifts, residual dipolar couplings, dipole-dipole Curie spin cross-correlation, and paramagnetic relaxation enhancements. The present study draws attention to a cross-correlation effect between nuclear relaxation due to anisotropic chemical shielding (CSA) and due to the anisotropic dipolar shielding (DSA) caused by the electronic Curie spin. This CSA x DSA cross-correlation contribution seems to have been overlooked in previous interpretations of paramagnetic relaxation enhancements. It is shown to be sufficiently large to compromise the 1/r6 distance dependence usually assumed. The effect cannot experimentally be separated from auto-correlated DSA relaxation. It can increase or decrease the observed paramagnetic relaxation enhancement. Under certain conditions, the effect can dominate the entire paramagnetic relaxation, resulting in nuclear resonances narrower than in the absence of the paramagnetic center. CSAxDSA cross-correlation becomes important when paramagnetic relaxation is predominantly due to the Curie rather than the Solomon mechanism. Therefore the effect is most pronounced for relaxation by metal ions with large magnetic susceptibility and fast-relaxing electron spin. It most strongly affects paramagnetic enhancements of transverse relaxation in macromolecules and of longitudinal relaxation in small molecules.     

Modulation of the distance dependence of paramagnetic relaxation enhancements by CSA x DSA cross-correlation

Paramagnetic metal ions with fast-relaxing electronic spin and anisotropic susceptibility tensor provide a rich source of structural information that can be derived from pseudo-contact shifts, residual dipolar couplings, dipole-dipole Curie spin cross-correlation, and paramagnetic relaxation enhancements. The present study draws attention to a cross-correlation effect between nuclear relaxation due to anisotropic chemical shielding (CSA) and due to the anisotropic dipolar shielding (DSA) caused by the electronic Curie spin. This CSA x DSA cross-correlation contribution seems to have been overlooked in previous interpretations of paramagnetic relaxation enhancements. It is shown to be sufficiently large to compromise the 1/r6 distance dependence usually assumed. The effect cannot experimentally be separated from auto-correlated DSA relaxation. It can increase or decrease the observed paramagnetic relaxation enhancement. Under certain conditions, the effect can dominate the entire paramagnetic relaxation, resulting in nuclear resonances narrower than in the absence of the paramagnetic center. CSAxDSA cross-correlation becomes important when paramagnetic relaxation is predominantly due to the Curie rather than the Solomon mechanism. Therefore the effect is most pronounced for relaxation by metal ions with large magnetic susceptibility and fast-relaxing electron spin. It most strongly affects paramagnetic enhancements of transverse relaxation in macromolecules and of longitudinal relaxation in small molecules.     

New mechanism of the spin-galvanic effect

A mechanism of the spin-galvanic effect associated with spin-dependent scattering is proposed. The electrical current in a system of spin-polarized two-dimensional carriers is induced due to interference of spin-preserving scattering processes and spin relaxation processes. The spin-galvanic effect is studied for heterostructures with the Elliott-Yafet and Dyakonov-Perel spin relaxation mechanisms. The proposed contribution to the spin-galvanic current may be dominant in A₃B₅ asymmetric quantum wells.     

Electron spin relaxation of radicals in γ-irradiated malonic acid and methyl malonic acid

Radicals generated by γ-irradiation of malonic acid and methyl malonic acid were studied as a function of temperature by inversion recovery, echo-detected saturation recovery and electron-electron double resonance (ELDOR) at X-band, and by continuous-wave saturation recovery at X-band and S-band. ELDOR reductions for malonic acid radical in polycrystalline and single-crystal samples indicate that nuclear spin relaxation is faster than both electron spin relaxation and cross relaxation between 93 and 233 K. Deuteration of the carboxylate protons caused the maximum ELDOR reduction to shift from about 110 to 150 K, consistent with the assignment of the rapid nuclear spin relaxation to hydrogen-bonded proton dynamics. ELDOR enhancements for both radicals formed in methyl malonic acid indicate that cross relaxation is faster than both electron spin relaxation and nuclear spin relaxation between 77 and 220 K. Enhanced cross relaxation and electron spin relaxation are attributed to the rotation of methyl groups at a rate comparable to the electron Larmor frequency. The temperature dependence of the enhancement of 1/T _1e was analyzed to determine the activation energies for methyl rotation. The same radical is formed in irradiated methyl malonic acid and L-alanine, but the barrier to rotation of the α-methyl is 500 K in the methyl malonic acid host and 1500 K in the L-alanine host, which indicates a large impact of the lattice on the barrier to rotation.     

半导体中的自旋弛豫--从体材料到量子阱、量子线、量子点

本文对半导体中的自旋弛豫过程给出一个简要的回顾,介绍了半导体材料从体材料到量子阱、量子线、量子点不同维数的结构中各种自旋弛豫过程,主要关注了自旋去相位和相干控制。对于不同材料中的各种弛豫机制,关注的重点在于如何能够在实验上以一种可以控制的方式来改变可调参数从而达到控制自旋弛豫过程。这些参数主要有电场、磁场、温度、应变、有效g因子等等。本文的组织上,首先介绍研究前景,第1部分简要介绍了自旋弛豫的四种机制。第2部分按照维数的不同将半导体中自旋弛豫分为3个部分:体材料、量子阱、量子线、量子点,在每一部分中又基本上按照电子、空穴、激子的顺序进行了简要的总结:对于不同的载流子,考虑了自旋弛豫对可调参数的依赖关系。这些结果要么试图解释了已有的实验结果,要么从理论上给出预言从而给实验指明了方向,为室温下可以使用的自旋电子学器件设计提供了依据,为固态量子计算和量子信息处理铺平了道路。最后简单地给出展望。     

半导体中的自旋弛豫——从体材料到量子阱、量子线、量子点

本文对半导体中的自旋弛豫过程给出一个简要的回顾,介绍了半导体材料从体材料到量子阱、量子线、量子点不同维数的结构中各种自旋弛豫过程,主要关注了自旋去相位和相干控制。对于不同材料中的各种弛豫机制,关注的重点在于如何能够在实验上以一种可以控制的方式来改变可调参数从而达到控制自旋弛豫过程。这些参数主要有电场、磁场、温度、应变、有效g因子等等。本文的组织上,首先介绍研究前景,第1部分简要介绍了自旋弛豫的四种机制。第2部分按照维数的不同将半导体中自旋弛豫分为3个部分:体材料、量子阱、量子线、量子点,在每一部分中又基本上按照电子、空穴、激子的顺序进行了简要的总结:对于不同的载流子,考虑了自旋弛豫对可调参数的依赖关系。这些结果要么试图解释了已有的实验结果,要么从理论上给出预言从而给实验指明了方向,为室温下可以使用的自旋电子学器件设计提供了依据,为固态量子计算和量子信息处理铺平了道路。最后简单地给出展望。     

Spin relaxation mechanism of hopping transport in a 2D asymmetric quantum dot array

Spin relaxation is studied in the hopping conduction mode in 2D arrays of quantum dots (QDs) with structural asymmetry. It is shown that the absence of the “up-down” symmetry in a QD leads to the emergence of a new spin relaxation mechanism in tunneling in a 2D QD array. The difference in spin relaxation mechanisms for symmetric and asymmetric QDs is demonstrated on the basis of theoretical analysis of an elementary event (jump between two tunnel-coupled dots). It is shown that spin flip during tunneling between QDs is the main spin relaxation mechanism in the transport in dense arrays of QDs in Ge placed in weak (1–10 T) magnetic fields.     

Spin fluctuations in the magnetic superconductor Y9Co7

The experimental data of magnetisation, Curie temperature and spin-lattice relaxation time for the magnetic superconductor Y₉Co₇ were analysed in the frame of the recently developed magnetic spin fluctuation models. The basic parameters of the models and the relaxation frequency function of a spontaneous spin fluctuation were calculated.     

Spin lattice relaxation rates of tunnelling CD3 groups

The spin lattice relaxation rates of deuterated methyl groups are calculated for threefold and sixfold potentials. It is shown that it should be possible to determine the symmetry of the potential hindering the methyl groups from deuteron spin lattice relaxation experiments. The temperature dependence of the spin lattice relaxation rates is discussed using a simple model. The similarities and the differences between proton NMR and deuteron NMR are pointed out. The main difference is thatEaEb transitions are forbidden by spin selection rules in case of CH₃, but not for CD₃. Therefore, and due to the fact that the quadrupolar interaction is a single particle interaction, deuteron NMR allows the study of the rotational dynamics of single methyl groups.     

Electron spin-lattice relaxation in radicals containing two methyl groups,generated by gamma-irradiation of polycrystalline solids

The effects of methyl rotation on electron spin-lattice relaxation times were examined by pulsed electron paramagnetic resonance for the major radicals in gamma-irradiated polycrystalline alpha-amino isobutyric acid, dimethyl-malonic acid, and L-valine. The dominant radical is the same in irradiated dimethyl-malonic acid and alpha-amino isobutyric acid. Continuous wave saturation recovery was measured between 10 and 295 K at S-band and X-band. Inversion recovery, echo-detected saturation recovery, and pulsed electron-electron double resonance (ELDOR) data were obtained between 77 and 295 K. For the radicals in the three solids, recovery time constants measured by the various techniques were not the same, because spectral diffusion processes contribute differently for each measurement. Hyperfine splitting due to the protons of two methyl groups is resolved in the EPR spectra for each of the samples. Pulsed ELDOR data were obtained to characterize the spectral diffusion processes that transfer magnetization between hyperfine lines. Time constants were obtained for electron spin-lattice relaxation (T(1e)), nuclear spin relaxation (T(1n)), cross-relaxation (T(x1)), and spin diffusion (T(s)). Between 77 and 295 K rapid cross-relaxation (deltaM(s) = +/- 1, deltaM(I) = -/+ 1) was observed for each sample, which is attributed to methyl rotation at a rate that is approximately equal to the electron Larmor frequency. The large temperature range over which cross-relaxation was observed suggests that methyl groups in the radical and in the lattice, with different activation energies for rotation, contribute to the rapid cross-relaxation. Activation energies for methyl and amino group rotation between 160 and 1900 K (1.3-16 kJ/mol) were obtained by analysis of the temperature dependence of 1/T(1e) at S-band and X-band in the temperature intervals where the dynamic process dominates T(1e).     

Proton spin relaxation in bisphenol-a polycarbonate,butyl rubber,and their composites

Proton spin-lattice relaxation times of bisphenol-A polycarbonate, butyl rubber, and blends of the two polymers were studied at 18 Mc/sec in the temperature range 90°-450°K. The proton spin-lattice relaxation is primarily dipolar in each polymer, due to methyl group reorientation and to reorientation of chain segments. In a blend of bisphenol-A polycarbonate with 7 and 10 wt of butyl, a nonexponential decay of magnetization was observed in the temperature range 280°-380°K. This was explained by the existence of two spin temperatures in these blends, indicating that processes which bring about the equilibrium within the spin system are slow compared to the spin-lattice relaxation times of the two components of the blend.     

Cross correlation between the dipole-dipole interaction and the Curie spin relaxation: the effect of anisotropic magnetic susceptibility

Cross-correlated relaxation caused by the interference of nuclear dipole-dipole interaction and the Curie spin relaxation (DD-CSR cross relaxation) is generalized to treat the case of anisotropic magnetic susceptibility, including the important case where the latter originates from zero-field splitting. It is shown that the phenomenon of DD-CSR cross relaxation is absolutely general and to be expected under any electronic configuration. The results of the generalization are presented for a model system, and the consequences for paramagnetic metalloproteins are illustrated with an example of cerium(III)-substituted calbindin. The effects of the magnetic anisotropy are found to be substantial.     

Spin dynamics from majorana fermions

Using the Majorana fermion representation of spin-1/2 local moments, we show how the dynamic spin correlation and susceptibility are obtained directly from the one-particle Majorana propagator. We illustrate our method by applying it to the spin dynamics of a nonequilibrium quantum dot, computing the voltage-dependent spin relaxation rate and showing that, at weak coupling, the fluctuation-dissipation relation for the spin of a quantum dot is voltage dependent. We confirm the voltage-dependent Curie susceptibility recently found by Parcollet and Hooley [Phys. Rev. B 66, 085315 (2002)]].     

EPR Study of Sc<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Nd<Superscript>143</Superscript> Isotopically Pure Impurity Crystals

The Sc₂SiO₅ single crystals doped with 0.001 at.% of the ¹⁴³Nd³⁺ ion were studied by continuous-wave and pulse electron paramagnetic resonance methods. The g-tensors and hyperfine structure tensors for two magnetically non-equivalent Nd ions were obtained. The spin–spin and spin–lattice relaxation times were measured at 9.82 GHz in the temperature range from 4 to 10 K. It was established that three relaxation processes contribute to the spin–lattice relaxation processes. There are one-phonon spin–phonon interaction, two-phonon Raman interaction and two-phonon Orbach–Aminov relaxation processes. It was established that spin–spin relaxation time is of the same magnitude for neodymium ion doped in Sc₂SiO₅ and in Y₂SiO₅.     

Goldstone mode relaxation in a quantum hall ferromagnet due to hyperfine interaction with nuclei

Spin relaxation in quantum Hall ferromagnet regimes is studied. As the initial non-equilibrium state, a coherent deviation of the spin system from the B direction is considered and the breakdown of this Goldstone-mode state due to hyperfine coupling to nuclei is analyzed. The relaxation occurring non-exponentially with time is studied in terms of annihilation processes in the “Goldstone condensate” formed by “zero spin excitons”. The relaxation rate is calculated analytically even if the initial deviation is not small. This relaxation channel competes with the relaxation mechanisms due to spin-orbit coupling, and at strong magnetic fields it becomes dominating.     

Mechanism of relaxation enhancement of spin labels in membranes by paramagnetic ion salts: dependence on 3d and 4f ions and on the anions

Progressive saturation EPR measurements and EPR linewidth determinations have been performed on spin-labeled lipids in fluid phospholipid bilayer membranes to elucidate the mechanisms of relaxation enhancement by different paramagnetic ion salts. Such paramagnetic relaxation agents are widely used for structural EPR studies in biological systems, particularly with membranes. Metal ions of the 3d and 4f series were used as their chloride, sulfate, and perchlorate salts. For a given anion, the efficiency of relaxation enhancement is in the order Mn(2+) > or = Cu(2+) > Ni(2+) > Co(2+) approximately Dy(3+). A pronounced dependence of the paramagnetic relaxation enhancement on the anion is found in the order ClO(-)(4) > Cl(-) > SO(2-)(4). This is in the order of the octanol partition coefficients multiplied by spin exchange rate constants that were determined for the different paramagnetic salts in methanol. Detailed studies coupled with theoretical estimates reveal that, for the chlorides and perchlorates of Ni(2+) (and Co(2+)), the relaxation enhancements are dominated by Heisenberg spin exchange interactions with paramagnetic ions dissolved in fluid membranes. The dependence on membrane composition of the relaxation enhancement by intramembrane Heisenberg exchange indicates that the diffusion of the ions within the membrane takes place via water-filled defects. For the corresponding Cu(2+) salts, additional relaxation enhancements arise from dipolar interactions with ions within the membrane. For the case of Mn(2+) salts, static dipolar interactions with paramagnetic ions in the aqueous phase also make a further appreciable contribution to the spin-label relaxation enhancement. On this basis, different paramagnetic agents may be chosen to optimize sensitivity to different structurally correlated interactions. These results therefore will aid further spin-label EPR studies in structural biology.     

Nonexponential 1H spin–lattice relaxation and methyl group rotation in molecular solids

We report a quantitative measure of the nonexponential ¹H spin–lattice relaxation resulting from methyl group (CH₃) rotation in six polycrystalline van der Waals solids. We briefly review the subject in general to put the report in context. We then summarize several significant issues to consider when reporting ¹H or ¹⁹F spin–lattice relaxation measurements when the relaxation is resulting from the rotation of a CH₃ or CF₃ group in a molecular solid.     

Relaxation of a quadrupolar nucleus in a strong magnetic field

Longitudinal relaxation of spin systems (S = 1, 3/2, 3) containing isolated quadrupolar nuclei are studied. The characteristic features of the relaxation behavior are identified in strong magnetic fields in the presence of chemical shift anisotropy. Two mechanisms are established that favor involvement of high rank multipoles in the relaxation process: an autocorrelation mechanism and a cross correlation mechanism. Multipoles of odd rank are involved in the relaxation of nuclei with spin S > 1 as a result of the autocorrelation mechanism (in this case, due to quadrupole interactions). The cross correlation mechanism, due to correlations between the chemical shift anisotropy and the quadrupole interactions, favors the appearance of multipoles of even rank. Expressions are presented for the multipole cross relaxation and longitudinal relaxation rates for spin systems with S = 1, 3/2, 3. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 18–25, January–February, 2006.     

N.M.R. gas to dilute solution chemical shifts for hexafluorobenzene

Studies of ¹H, ¹³C, ¹²⁵Te, ¹²³Te relaxation rates in liquid dimethyltelluride were carried out. Relaxation mechanisms have been separated for all four studied nuclei. Tellurium relaxation was found to be strictly dominated by spin rotation, while for ¹H and ¹³C, dipole-dipole and spin rotation interactions exist simultaneously. Reorientation of methyl groups about their symmetry axis was found to be approximatively of the same rate as the overall molecular motion.