Electron spin relaxation time measurements using radiofrequency longitudinally detected ESR and application in oximetry

Longitudinally detected ESR (LODESR) involves transverse ESR irradiation with a modulated source and observing oscillations in the spin magnetization parallel to the main magnetic field. In this study, radiofrequency-LODESR was used for oximetry by measuring the relaxation times of the electron. T1e and T2e were measured by investigating LODESR signal magnitude as a function of detection frequency. We have also predicted theoretically and verified experimentally the LODESR signal phase dependence on detection frequency and relaxation times. These methods are valid even for inhomogeneous lines provided that T1e>T2e. We have also developed a new method for measuring T1e, valid for inhomogeneous spectra, for all values of T1e and T2e, based on measuring the spectral area as a function of detection frequency. We have measured T1e and T2e for lithium phthalocyanine crystals, for the nitroxide TEMPOL, and for the single line agent Triarylmethyl (TAM). Furthermore, we have collected spectra from aqueous solutions of TEMPOL and TAM at different oxygen concentrations and confirmed that T1e values are reduced with increased oxygen concentration. We have also measured the spin-lattice electronic relaxation time for degassed aqueous solutions of the same agents at different agent concentrations. T1e decreases as a function of concentration for TAM while it remains independent of free radical concentration for TEMPOL, a major advantage for oxygen mapping. This method, combined with the ability of LODESR to provide images of exogenous free radicals in vivo, presents an attractive alternative to the conventional transverse ESR linewidth based oximetry methods.     

In vivo oximetry by a pulsed longitudinally detected ESR spectrometer

By using a narrow single electron spin resonance (ESR) line agent, triarylmethyl, tris(8-carboxy-2,2,6,6-tetrahydroxyethylbenzo[1,2-d:4,5-d′] bis(1,3)dithiole-4-yl)methyl sodium salt (TAM OX063), pulsed longitudinally detected ESR (LODESR) measurements of a phantom or the chest of a living mouse at the operating frequency of ca. 300 MHz were taken and the effective longitudinal relaxation time (T ₁^*) was estimated for oximetry. Under irradiation of a pair of π-pulses with a variable interval between pulses (τ), in-phase LODESR signal intensities were obtained from the phantoms containing TAM dissolved in a physiological saline solution at a concentration of 1 mM and various concentrations of oxygen. TheT ₁^* of the phantom was calculated from the plotted curve of the LODESR signal intensity against τ. It was found that the reciprocal ofT ₁^*, i.e., the longitudinal relaxation rate, increased with the concentration of oxygen. In vivo pulsed LODESR measurements of the chest of living mice that had received a TAM injection via the intraperitoneal route were made. While the LODESR measurements were being made, the mice in one group breathed normal air and those in another group breathed 100% oxygen. It was found that the longitudinal relaxation rate of the mice breathing 100% oxygen was significantly greater than that of mice breathing normal air, indicating that breathing 100% oxygen elevates the thoracic longitudinal relaxation rate.     

Spin relaxation of quadrupole nuclei in paramagnetic and magnetically ordered insulators

The longitudinal and transverse spin relaxation through a (generally anisotropic) electron-nucleus interaction in paramagnetic and magnetically ordered insulators is theoretically studied for nuclei with a resolved quadrupole structure. Expressions are derived for the relaxation rates of both the transverse nuclear magnetization components when individual transitions are excited in the quadrupole structure and the total longitudinal nuclear magnetization component. These expressions are reduced to a form that contains the Fourier transforms of the time correlation functions only for the electron spins. Given the specific form of these correlation functions corresponding to different phase states of the electron spins and different origins of their fluctuations, the temperature dependences of the nuclear relaxation rates are ascertained in various cases, including those for dipole and isotropic hyperfine interactions. Calculations are performed for arbitrary electron and half-integer nuclear spins by taking into account the possible quadrupole splitting of the NMR spectrum without any restriction on the smallness of the ratio ?ω s/k_BT (ω_s is the resonance frequency of the electron spins). The derived expressions are compared with available experimental data on the longitudinal and transverse nuclear relaxation in colossal-magnetoresistance lanthanum manganites in the part of their phase diagram where the corresponding samples are either paramagnetic or magnetically ordered insulators and near the points of transition to an ordered state. Interpretations alternative to the existing ones are offered.     

Non-Markovian theory of electron paramagnetic resonance in localized and quasi-localized electron spins via an example of manganites with colossal magnetoresistance

An approach based on the memory functions formalism is applied to derive non-Markovian equations of motion for the magnetization components of localized and quasi-localized electron spins under electron paramagnetic resonance (EPR) conditions using the example of manganites with colossal magnetoresistance. General Hasegawa-Bloch-type equations are applied to describe certain experimental data concerning the shape and the width of EPR lines and the longitudinal and transverse relaxation rates. Particular cases of these equations reproduce well-known theoretical results concerning EPR in manganites with colossal magnetoresistance. The results obtained explain certain well-known experimental phenomena and may stimulate further research.     

A multilayered element resonator for CW-ESR and longitudinally detected ESR at radio frequency

The design and evaluation of a multilayered element resonator (MLR), which consists of multiple layers of half-loop conductor plates and insulator sheets, are presented. An MLR and a bridge shielded loop-gap resonator (BLGR), which have similar sizes and resonant frequencies, were fabricated to compare their performances. Using the MLR and the BLGR, the modulation field width and signal intensity of a phantom containing a nitroxide radical were measured by employing a continuous-wave electron spin resonance (CW-ESR) technique at a radio frequency of 300 MHz. Using the same resonators, the longitudinally detected ESR (LODESR) signal intensities of the phantom were also compared. The loadedQ values of the resonators were almost the same. The modulation widths in the MLR were significantly wider than those in the BLGR when the modulation coils were driven at the same voltage. The signal intensities of CW-ESR and LODESR from the phantom in the MLR were significantly greater than those from the BLGR. Since eddy currents disturb the penetration of the modulation field in CW-ESR or detection of changes in magnetization in LODESR observations, these results show that, in the MLR, the eddy currents were suppressed to a greater degree than in the BLGR.     

Electron paramagnetic resonance in impure superconductors of the second kind under conditions of fluctuation pairing of conduction electrons

Coupled equations are obtained for the transverse dynamic susceptibilities of paramagnetic impurities and conduction electrons in an impure superconductor of the second kind in a magnetic field somewhat higher than the upper critical field H_c2 under the conditions of fluctuation pairing of the conduction electrons. The fluctuation corrections to the shift and line-width of the magnetic resonance are determined in the paramagnetic impurities and the conduction electrons. The magnetic resonance parameters are investigated under the conditions of coupled motion of the magnetic moments of the impurities and the conduction electron spins in the presence of superconducting fluctuations.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 41–45, August, 1978.     

Oxygen effect on spin relaxation of the surface paramagnetic centers in carbon chars

The original technique with the use of longitudinal electron paramagnetic resonance detection was applied to measure longitudinal and transversal electron relaxation times (T ₁ andT ₂) in specially prepared carbon chars containing paramagnetic centers (PCs) on the surface. The results not only confirmed the conclusions of our previous studies but enabled us to determine the exchange integral and clarify the mechanism of interaction between the PCs and adsorbed molecular oxygen O₂. A spin relaxation mechanism was also suggested which takes into account both the exchange and dipolar interactions in the systems combining PC and O₂. The value of the exchange integral between PCs as well as its functional dependence on the oxygen content were estimated.     

Self-induced acoustic transparency in the long-short-wave resonance mode

The effect of self-induced acoustic transparency for transverse-longitudinal pulses propagating along an external magnetic field in a system of resonance paramagnetic impurities with the effective spin S=1/2 is theoretically investigated. In this case, the short-wave transverse component of the pulse causes quantum transitions, and the longitudinal long-wave component dynamically shifts the frequency of those transitions. When the speeds of the longitudinal and transverse acoustic waves in the crystal matrix are close to each other, both components interact in the mode of the long-short-wave resonance, which is described by a system of nonlinear integro-differential equations. It is shown that this interaction results, in particular, in the modulation of the carrier frequency of the circular-polarized component of the pulse. More precisely, the frequency in the neighborhood of the signal’s maximum is less than in the vicinity of its edges. Solutions in the form of traveling 2π-pulses are analyzed analytically and numerically. It is shown that there exist solutions that include a longitudinal component and cannot be reduced to well-known transverse solitons of the sinus-Gordon equation.     

Absorption line CW EPR using an amplitude modulated longitudinal field

In standard continuous wave electron paramagnetic resonance (CW-EPR) experiments, the first derivative of absorption lines is detected. This type of a line shape is caused by the magnetic field modulation and is usually an undesired feature, since the sensitivity of CW-EPR drastically decreases with increasing linewidth. A new approach is introduced, which allows for the measurement of absorption line EPR spectra in systems with broad inhomogeneous lines. The method makes use of multiple-photon transitions that are induced in spin systems when a transverse microwave and a longitudinal radio frequency field are simultaneously applied. The absorption lines are obtained by using amplitude modulation of the radio frequency field and slight saturation of the spectral lines. The basics of the new approach are discussed and experimental examples are given.     

Coupled (localized+delocalized) electron spins dynamics in polymer phase of RbC60 fulleride

The transverse response (transverse dynamic susceptibility) of coupled localized (s) and delocalized (e) electron spins of a metal paramagnet as well as the longitudinal dynamic response of such a system (to be registered by a longitudinal coil) to the modulation of microwave power saturating electron spin resonance (ESR) are calculated. The ESR spectrum is analytically decomposed into two Lorentzians with normal resonance frequencies and decay rates of the coupled localized +delocalized electron spin system. In the case of relaxationally coupled s- and e-spins the longitudinal response is decomposed into two “relaxational” Lorentzians squared with amplitudes containing ESR lineshapes with above-mentioned shifted frequencies and linewidths as well as enhancement-suppression coefficients of magnetization evolution. These results are essential for the interpretation of experiments on longitudinal response in metal paramagnets, the latter being the source of important information on longitudinal electron relaxation; in particular, for extraction of information from longitudinal response experiments in the polymer phase of RbC₆₀ fullende, where the obtained results describe the observed form of the ESR spectrum and the main features of the longitudinal response.     

On the soliton-like dynamics of ultrashort acoustic pulses in a paramagnetic crystal

A system of nonlinear equations describing the dynamics of the longitudinal and transverse components of an acoustic pulse in a cubic crystal containing paramagnetic impurities has been obtained. On the basis of this system, the dynamics of a two-component ultrashort acoustic pulse propagating under the Zakharov-Benney resonance conditions has been analytically investigated.     

Spin response in nonlocal nonlinear optics

A novel effect of the electron spin in nonlinear optics is predicted. Starting from the Pauli Hamiltonian, we present the influence of the electron spin on the nonlinear optical response of a homogeneous electron gas in the low temperature limit. It is shown that the longitudinal second-harmonic response which results from a transverse incoming field differs significantly from the usual paramagnetic response when spin effects are included. The calculation is done both with and without screening.     

Acoustic activity effect for picosecond soliton-like pulses

A theoretical analysis is made of the acoustic activity for interfering picosecond acoustic soliton-like pulses of down to a single oscillation period. An analysis is made of the case where these pulses propagate parallel to an external magnetic field and one of the acoustic axes in a cubic crystal containing paramagnetic impurities having effective spin S = 1. Allowance is made for natural, magnetic (Faraday), and cross acoustic activity. This cross activity is caused by the significant spatial nonlocality of the spin-phonon interaction for such short pulses in crystals having no center of inversion in the presence of paramagnetic impurities. A system of nonlinear equations is obtained for the transverse and longitudinal components of the strain in the form of a coupling between the “differentiated” nonlinear Schrödinger equation (with nonlinearity after the derivative sign) and the Korteweg-de Vries equation which generalizes the known systems of long-short-wavelength resonance to the case where the slowly varying envelope approximation is not valid. An approximate solution of this system is used to study the structure of an elastic soliton-like pulse whose transverse component has a rotating plane of polarization, which propagates under conditions of nonlinear coupling with the longitudinal strain.     

A CT using longitudinally detected ESR (LODESR-CT) of intraperitoneally injected nitroxide radical in a rat's head

We have developed an in vivo longitudinally detected ESR (LODESR) imaging system operating at 700 MHz based on a loop-gap resonator and a pair of saddle-type pickup coils. A good linear relationship between the LODESR signal intensity and the applied power in a range up to 15.8 W was obtained. The detection of LODESR signals was barely affected by variations in the resonant properties. The characteristic of LODESR is suitable for in vivo examination. Using this system, we succeeded in obtaining LODESR-CT images of the head region of a rat after the intraperitoneal injection of a nitroxide radical.     

A multi-frequency EPR spectroscopy approach in the detection of boson peak excitations

The influence of boson peak (BP) excitations on low-temperature spin-lattice relaxation rate of a paramagnetic center embedded in a glassy matrix is investigated in the context of multi-frequency electron paramagnetic resonance (EPR) detection. In the theoretical analysis, the transition rate of spin one-half in the presence of a phonon field is calculated within the approximation of Fermi's golden rule. Several phonon densities of states are compared, among which one originating from a model of quasi-localized vibrations has been introduced into electron spin relaxation formalism for the first time. The respective frequency dependencies of spin-lattice relaxation rates are predicted which should lead to observable effects of BP modes if a multi-frequency study at very low temperatures is performed.     

Self-induced acoustic transparency of three-component longitudinal-transverse pulses

The features of the nonlinear dynamics of three-component elastic pulses in a low-temperature crystal containing paramagnetic impurities of electron and nuclear spins have been analyzed in the slowly varying envelope approximation. The presence of the electron spin subsystem makes it possible to equate the velocities of longitudinal sound and transverse acoustic waves; as a result, all components of the strain field efficiently interact with each other through the nuclear spin subsystem. The system of equations for envelopes of harmonics of the components of the strain field and the spin variables has been derived. The relations between the amplitudes and phases of the components have been obtained, the spectral composition has been analyzed, and the regimes of acoustic transparency of three-component longitudinal-transverse pulses have been discussed.     

A first study of dielectronic recombination with the super-expanded electron beam in CRYRING

A first temperature measurement of the expanded electron beam from a super-conducting magnet in the cooler of CRYRING is reported. It is based on detection of a dielectronic recombination resonance in C²⁺. For this measurement C³⁺ was stored in the ring at 3 rm{MeV/amu} energy. A fit to the resonance with free transverse and longitudinal temperatures gave 3.9 × 10^-3 eV and 4.5 × 10^-5 eV, respectively. The result is also compatible with the values of 10^-3 eV for the transverse and 6.7 ×10-5 eV for the longitudinal component, in good agreement with expected values. This revised version was published online in July 2006 with corrections to the Cover Date.     

Estimates of the electron density in an ECR source of calcium plasma

A technique is proposed for estimating parameters of the plasma produced by a source based on the electron cyclotron resonance. The analysis is made for the ion cyclotron resonance (ICR) facility designed for separating calcium isotopes. It is assumed that the resonance condition for an extraordinary wave is fulfilled for electrons moving towards the wave. The plasma optical thickness, the transverse energy of resonance electrons, and its dependence on the longitudinal velocity are determined. The charged particle density in the plasma flow is estimated in terms of the balance of the electrons generated as a result of vapor ionization in the discharge zone and the electron losses due to longitudinal ambipolar diffusion.     

Observation of faraday waves in a Bose-Einstein condensate

Faraday waves in a cigar-shaped Bose-Einstein condensate are created. It is shown that periodically modulating the transverse confinement, and thus the nonlinear interactions in the BEC, excites small amplitude longitudinal oscillations through a parametric resonance. It is also demonstrated that even without the presence of a continuous drive, an initial transverse breathing mode excitation of the condensate leads to spontaneous pattern formation in the longitudinal direction. Finally, the effects of strongly driving the transverse breathing mode with large amplitude are investigated. In this case, impact-oscillator behavior and intriguing nonlinear dynamics, including the gradual emergence of multiple longitudinal modes, are observed.     

Interaction of electromagnetic waves with nonlinear substance layer under conditions of electron paramagnetic resonance in millimeter waves

Trancated equations have been obtained by the Green's functions method for a slowly varying amplitude of a transverse magnetic field component in a paramagnetic layer under conditions of the electron paramagnetic resonance (EPR). A magnetic susceptibiliti of the substence has been found from the Bloch equation for a homogeneously line breadth of the EPR. In a stationary case a solution of a nonlinear boundary-value problem is redused to a solution of two boundary problems for amplitude and phase equations. It is shown that unstable regimes of the electrodynamic system under inves tigation are possible.Electrodynamic characteristics of a nonlinear resonator of the Fabry-Pero type filled with a saturated paramagnetic medium have been analyzed numerically in a non-stationery case.