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.     

Properties of the HYSCORE spin echo signal

In hyperfine sublevel correlation spectroscopy (HYSCORE), the finite duration of the microwave pulses leads to an incomplete inversion of the electron spin magnetization by the third pulse, which results in a significant admixture of stimulated ESEEM to HYSCORE ESEEM. This virtually unavoidable contribution of stimulated ESEEM seriously hampers the analysis of the modulation amplitudes in HYSCORE. In this work, we analyze the properties of the spin echo signals contributing to the composite HYSCORE signal. Based on this analysis, we propose the strategies of HYSCORE data acquisition and processing that allow one to practically eliminate the contribution of the stimulated echo and make the HYSCORE ESEEM analyzable in quantitative terms.     

Study of proton spin echoes in the nematic liquid crystalline phase

We studied spin echoes formed in the nematic crystalline phase using 90°- τ-β pulse sequence, where τ is the time between pulses and β the rotation produced by the second pulse. The decay of the echoes as a function of 2τ is nearly exponentail with a time constant T_E. Both T_E and the echo amplitude at a fixed τ were studied as a function of β in two nematics.     

Electron spin relaxation by spin-rotation interaction in benzoyl and other acyl type radicals

In various studies of the spin dynamics in radical pairs, benzoyl-type radicals have been one of the two paramagnetic pair species. Their electron spin relaxation has been assumed to be slow enough to be neglected in the data analysis. This assumption is checked by measuring the electron spin relaxation in a sequence of three acyl radicals (benzoyl, 2,4,6-trimethylbenzoyl and hexahydrobenzoyl) by time-resolved electron paramagnetic resonance spectroscopy. In contrast to the assumed slow relaxation, rather short spin-lattice relaxation times (100–400 ns) are found for benzoyl and 2,4,6-trimethylbenzoyl radicals from the decay of the integral initial electron polarization to thermal equilibrium at different temperatures and viscosities. The relaxation is induced by a spin-rotation coupling arising from two different types of radical movements: overall rotation of the whole radical and hindered internal rotation of the CO group. The predominant second contribution depends on the barrier of the internal rotation. The obtained results are well explained in the frame of Bull’s theory when using a modified rotational correlation time τ _J . The size of the spin-rotation coupling due to the internal CO group rotation in benzoyl radicals is estimated to be |C _α|=1510 MHz.     

130 GHz ESEEM induced by electron–electron interaction in biradical

A three-pulse stimulated ESE at 130 GHz (D-band) of nitroxide biradical in a molecular glass shows envelope modulation (ESEEM) when the time separation between the first and the second pulses is varied. This ESEEM originates from relaxation-induced flips of the spin partner during the mixing period between the second and third pulses. These flips alternates the local dipolar field in which the resonant spins precess before second and after third pulses. The ESEEM is different for different spectral positions, due to orientation selectivity. For toluene glassy solution at 35 K Fourier transform shows pronounced peak reflecting singularity of the Pake resonance pattern. Increasing temperature up to 80 K results in appearance of a strong additional peak ascribed to alteration of the resonance field induced by methyl group reorientation.     

Temperature Dependence of Electron Spin Relaxation of 2,2-Diphenyl-1-Picrylhydrazyl in Polystyrene

The electron spin relaxation rates for the stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) doped into polystyrene were studied by inversion recovery and electron spin echo at X-band and Q-band between 20 and 295 K. At low concentration (340 μM, 0.01 %), spin–lattice relaxation was dominated by the Raman process and a local mode. At high concentration (140 mM, 5 %), relaxation is orders of magnitude faster than at the lower concentration, and 1/T ₁ is approximately linearly dependent on the temperature. Spin lattice relaxation rates are similar at X-band and Q-band. The temperature dependence of spin echo dephasing was faster at about 140 K than at higher or lower temperatures, which is attributed to a wagging motion of the phenyl groups.     

Electron spin-lattice relaxation time and spectral diffusion in γ-irradiated l-alanine

We performed continuous (CW) wave and pulsed ESR experiments to obtain information on the relaxation behavior of the l-alanine radical in an irradiated single crystal. The analysis of the CW saturation behavior gives a relaxation time of 2.8 μs. The echo detected saturation recovery was obtained for a number of different experimental conditions. In any case only a portion of the 120 G wide ESR spectrum can be affected by the microwave (MW) pulses, spectral diffusion is active and a multi-exponential decay is therefore obtained. We measured characteristic spectral diffusion times of 1–10 and 20–50 μs. We found that a long time of about 200 μs can be measured only by using a train of long selective saturating pulses and short detecting pulses. The stimulated echo decay is bi-exponential, and the characteristic times are very short. A variable temperature investigation in the range 200 to 290 K showed that the decay is governed by the spectral diffusion and by the transverse nuclear spin relaxation timeT _2n of the methyl protons.     

Anomalous magnetism and 209Bi nuclear spin relaxation in Bi4Ge3O12 crystals

The quadrupole ²⁰⁹Bi spin–spin and spin–lattice relaxation were studied within 4.2–300 K for pure and doped Bi₄Ge₃O₁₂ single crystals which exhibit, as was previously found, anomalous magnetic properties. The results revealed an unexpectedly strong influence of minor amounts of paramagnetic dopants (0.015–0.5 mol.%) on the relaxation processes. Various mechanisms (quadrupole, crystal electric field, electron spin fluctuations) govern the spin–lattice relaxation time T ₁ in pure and doped samples. Unlike T ₁, the spin–spin relaxation time T ₂ for pure and Nd-doped samples was weakly dependent on temperature within 4.2–300 K. Doping Bi₄Ge₃O₁₂ with paramagnetic atoms strongly elongated T ₂. The elongation, although not so strong, was also observed for pure and doped crystals under the influence of weak (～30 Oe) external magnetic fields. To confirm the conclusion about strong influence of crystal field effects on the temperature dependence of T ₁ in the temperature range 4.2–77 K, the magnetization vs. temperature and magnetic field was measured for Nd- and Gd-doped Bi₄Ge₃O₁₂ crystals using a SQUID magnetometer. The temperature behavior of magnetic susceptibility for the Nd-doped crystal was consistent with the presence of the crystal electric field effects. For the Gd-doped crystal, the Brillouin formula perfectly fitted the curve of magnetization vs. magnetic field, which pointed to the absence of the crystal electric field contribution into the spin–lattice relaxation process in this sample.     

ESR, ENDOR, and ESEEM investigations on UV-irradiated 2,4,6-tri-tert-butyl phenol crystals

Electron spin resonance (ESR), electron nuclear double resonance (ENDOR), and electron spin echo envelope modulation (ESEEM) measurements were carried out for UV-irradiated 2,4,6-tri-tert-butyl phenol in the polycrystalline state. The radical produced in the crystal was detected by ESR and identified to be the corresponding phenoxyl radical, which is well characterized in the chemical oxidations in solutions. ENDOR and ESEEM spectra were unambiguously analyzed in terms of the hyperfine coupling constants determined from well-resolved ESR in solutions. Radical pairs in the crystals were also ascertained, and together with the single-crystal study the analysis disclosed zero-field splitting parameters in the triplet states. ESEEM time decays gave relaxation timesT ₁ = 5.94 andT ₂ = 1.12 μs at room temperature. These appropriate values permit an easy detection of the spin echoes, and therefore this radical matrix can be used as a useful standard for pulsed ESR investigations.     

Low-frequency NMR with a non-resonant circuit

General expressions describing the refocused stimulated (RS) and refocused virtual (RV) electron spin echo envelope modulations (ESEEM) generated with the same basic four-pulse sequence are derived. It is shown that integration of the 3D time domain trace over the two "low-resolution" time intervals (those between the first and second and between the third and fourth microwave pulses) results in a dead time-free 1D ESEEM trace in the "high-resolution" dimension (i.e., the time interval between the second and third microwave pulses) that only contains harmonics with the fundamental frequencies of nuclear transitions. The practical implementation of the integrated RS ESEEM requires pulse swapping, which leads to unrecoverable distortions in the ESEEM traces and the resulting spectra. The integrated RV ESEEM is free from such distortions and represents a robust practical technique for obtaining dead time- and blind spots-free spectra of nuclear transitions, without homonuclear combination lines. As an application example, the integrated RV ESEEM was used to obtain the spectrum of a strongly-coupled proton of the OH ligand of the Mo(V) active center of the low-pH form of the molybdoenzyme sulfite oxidase.     

NMR spin lattice relaxation in dilute CuFe alloys with impurity interactions

Previous measurements by Wilkening and Hesse have shown, that the excess relaxation rate ΔT^-1₁ of the matrix nuclei in $\text{CuF}$e dilute alloys can be explained in terms of the LD-model with rapid spin diffusion. Measurements reported in this paper confirm the existence of an electric quadrupole diffusion barrier. It could be shown that the influence of the quadrupole barrier is coupled to large clusters within the alloy. The electron spin lattice relaxation time τ₁ behaves temperature independent in the range 30 K ? T ? 300 K. This can be understood if an effective correlation time τ is introduced, which results from a distrubution of temperature dependent times τ^cl(T) belonging to clusters of different size.     

X-band Electron Spin Relaxation Times for Four Aromatic Radicals in Fluid Solution and Comparison with Other Organic Radicals

X-band electron spin relaxation times of BDPA (1:1 α,γ-bisdiphenylene-β-phenylallyl), galvinoxyl 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy, DPPH (2,2-diphenyl-1-picrylhydrazyl) and thianthrene radicals in fluid solution were measured by electron spin echo and inversion recovery at ambient temperature. Tumbling correlation times are estimated to be in the range of 20–30 ps. In this fast tumbling regime T ₁ ~ T ₂. Relaxation times are compared with previously reported values for symmetrically substituted triarylmethyl, semiquinone, and nitroxide radicals. The concentration dependence of spin lattice relaxation for neutral BDPA in toluene is about 10³ times greater than for anionic trityl radicals in water. T ₁ decreases in the order carbon-center BDPA > galvinoxyl > DPPH > thianthrene. The dominant relaxation mechanisms are proposed to be a local mode for BDPA, spin rotation, local mode and modulation of anisotropic proton hyperfine coupling for galvinoxyl, modulation of anisotropic nitrogen hyperfine for DPPH, and spin rotation plus modulation of anisotropic proton hyperfine coupling for thianthrene.     

Hole spin relaxation in Ge quantum dots

Hole spin relaxation in an isolated Ge quantum dot due to interaction with phonons is investigated. Spin relaxation in this case occurs through the mechanism of the modulation of the spin-orbit interaction by lattice vibrations. According to the calculations performed, the spin relaxation time due to direct single-phonon processes for the hole ground state equals 1.4 ms in the magnetic field H = 1 T at the temperature T = 4 K. The dependence of the relaxation time on the magnetic field is described by the power function H^?5. At higher temperatures, a substantial contribution to spin relaxation is made by two-phonon (Raman) processes. Because of this, the spin relaxation time decreases to nanoseconds as the temperature is raised to T = 20 K. Analysis of transition probabilities shows that the third and twelfth excited hole states, which are intermediate in two-step relaxation processes, play the main part in Raman processes.     

Peak suppression in ESEEM spectra of multinuclear spin systems

We have observed a disturbing suppression effect in three-pulse ESEEM and HYSCORE spectra of systems with more than one nucleus coupled to the electron spin. For such systems, the ESEEM signal contains internuclear combination peaks of varying intensity. At the same time, the peaks at the basic ESEEM frequencies are reduced in intensity, up to the point of complete cancellation. For both three-pulse ESEEM and HYSCORE, the amplitude of a peak of a given nucleus depends not only on its modulation depth parameter k and the tau-dependent blind-spot term b, but also on k and b of all other nuclei. Peaks of nuclei with shallow modulations can be strongly suppressed by nuclei with deep modulations. This cross-suppression effect explains the observation that HYSCORE (1)H peaks are often very weak or even undetectable in the presence of strong (14)N peaks. Due to this distortion of intensities, ESEEM spectra have to be analysed very carefully. We present a theoretical analysis of this effect based on the product rules, numerical computations, and illustrative experimental data on Cu(gly)(2). In experiments, the impact of this cross suppression can be alleviated by a proper choice of tau values, remote echo detection, and matched pulses.     

Multiple structure of two-pulse nuclear spin echo in cobalt films

The conditions for the formation of two-pulse echo signals from ⁵⁹Co nuclei in thin magnetic films at T=4.2 K are investigated. In the framework of the existing mechanisms, numerical simulation of the conditions for the formation of extra 3τ and 4τ echo signals (τ is the time delay between pulses) is carried out. It is shown that the multiple structure of the echo from ⁵⁹Co nuclei at T=4.2 K is due to a mechanism in which an additional hyperfine magnetic field proportional to nuclear magnetization is acting on the nuclear spin system.     

Multifrequency EPR of four triarylmethyl radicals

Continuous-wave spectra at W-band of four triarylmethyl (trityl) radicals at 100 K in 1∶1 water-glycerol exhibit rhombic electron paramagnetic resonance spectra. The rigid-lattice line widths at W-band are only 3 to 5 times larger than at X-band or S-band, and fluid-solution line widths are much narrower than those for rigid lattice, which indicates that unresolved anisotropic nuclear hyperfine couplings make significant contributions to the rigid-lattice line widths. Spin-flip lines are observed in glassy-solution spectra at X-band and S-band, but not at W-band or 250 MHz. At 100 KT _m is dominated by spin diffusion of solvent protons and is independent of microwave frequency. Between about 130 and 170 K, 1/T _m for trityl-CH₃ is enhanced by rotation of the methyl groups at a rate comparable to inequivalences in the hyperfine interaction. Motional averaging of anisotropic interactions enhances spin echo dephasing between about 200 and 300 K. The temperature dependence of 1/T ₁ is similar for the four radicals and is consistent with assignment of the Raman process and a local mode as the dominant relaxation processes. The similarity inT ₁ values at W-band and X-band supports this assignment.     

Proton spin relaxation of butenes and butane in CaNaA zeolites

Using nmr pulse techniques the temperature dependence of proton spin relaxation times T₁ and T₂ of n-butene and butane molecules adsorbed on CaNaA zeolites with different content of Ca⁺⁺ ions has been investigated. The observed diminution of correlation times with rising degree of Ca⁺⁺ exchange can only be explained if translational motions, i.e. jumps between the supercages, dominate the proton spin relaxation of the adsorbates. Peculiarities in the microdynamical behaviour of the various n-butenes are in accordance with the model of electrostatic interactions between molecular dipole moments and electric fields in A zeolites as proposed by Tempère and Imelik in order to explain the stereoselectivity of the isomerization of n-butenes in A zeolites. Applying Torrey's well-known theory of nmr relaxation as dominated by translational jumps with arbitrary lengths, the mean time between two subsequent jumps has been estimated. In combination with measurements of self-diffusion coefficients by Kärger and Renner, these values lead to mean jump lengths which are reasonable compared with the distance of two neighbouring large zeolitic cavities. In order to interpret the methyl reorientation which dominates the longitudinal proton spin relaxation of the adsorbed hydrocarbons at lower temperatures, a model for calculating the intermolecular contribution to the relaxation rate has been discussed.     

Distance determination in human ubiquitin by pulsed double electron-electron resonance and double quantum coherence ESR methods

Recently, distance measurements by pulsed ESR (electron spin resonance) have been obtained using pulsed DEER (double electron-electron resonance) and DQC (double quantum coherence) in SDSL (site directed spin labeling) proteins. These methods can observe long range dipole interactions (15-80A). We applied these methods to human ubiquitin proteins. The distance between the 20th and the 35th cysteine was estimated in doubly spin labeled human ubiquitin. Pulsed DEER requires two microwave sources. However, a phase cycle is not usually required in this method. On the other hand, DQC-ESR at X-band ( approximately 9GHz) can acquire a large echo signal by using pulses of short duration and high power, but this method has an ESEEM (electron spin echo envelope modulation) problem. We used a commercial pulsed ESR spectrometer and compared these two methods.     

Double electron-electron resonance in electron spin echo: Conformations of spin-labeled poly-4-vinilpyridine in glassy solutions

Double electron-electron resonance in electron spin echo has been used to study the glassy solutions of poly-4-vinylpyridine doped by nitroxyl radicals frozen in liquid nitrogen. The phase relaxation of spin labels due to spin-spin interaction of unpaired electrons has been studied. The intramolecular and intermolecular contributions of the dipole-dipole interaction of spin labels into relaxation process have been separated. It has been established that both the intramolecular and intermolecular spin-spin interaction of spin labels lead to the dependence of echo signal on timeT of the exp (?aT ^q ) type. It is shown that for the intramolecular interaction the experimentalq value is 0.3, for the intermolecular one it is 2. The assumption has been made of the linear structure of polymeric molecules due to the presence of a sufficiently high density of an electric charge on polymeric molecules.     

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.