Electron spin-echo envelope modulation at S-band. 1: Analysis of hyperfine interaction effects

Electron spin-echo techniques have been successfully applied to the study of disordered systems mainly due to the nuclear modulation of the echo signal, the analysis of which gives information on the structural arrangement around the paramagnetic center. Most applications to date have been carried out at X-band (≈9 GHz). Here we report on the analysis of two and three pulse modulation patterns simulated at S-band (≈3 GHz) for which the modulation depth is about tenfold deeper and more quantitative analysis ofI=1/2 nuclei becomes possible. The investigation is applied to two different nuclei of experimental interest at different electron-nucleus distances, and comparison is done with the corresponding X-band patterns.¹³C and¹⁵N nuclei, both with nuclear spin quantum valueI=1/2, are chosen due to their different nuclearg-factors that produce quite different modulation periods. Modulation features due to isotropic hyperfine couplings are also analyzed. It is shown that in several cases complicated patterns arise, that are successfully interpreted by Fourier transform in the frequency domain. Some conclusions are drawn concerning the experimental conditions under which the use of S-band is really of significant advantage with respect to X-band.     

Electron spin echo at S-band: Nuclear modulations and decay in C60 powder

At S-band (≈ 3 GHz) the modulation amplitude of the Electron Spin Echo patterns is increased with respect to the amplitude at X-band: as a consequence, it is possible to reveal the presence of nuclei not detectable at X-band. In this paper the results obtained by running ESE experiments at S-band on a C₆₀ powder sample containing radicals are shown and discussed. The two- and three-pulse Electron Spin Echo patterns exhibit both¹³C modulation and proton modulation not detected at X-band. The experimental data are quantitatively analyzed by simulating the time-domain patterns and their Fourier transforms. It results that a noticeable amount of proton nuclei surrounds the intrinsic paramagnetic centers. On the basis of the analysis, a possible explanation of their existence is given.     

Electron spin-echo envelope modulation at S-band. 3: Analysis of nuclear quadrupole interaction effects

In the present paper the nuclear modulation of electron spin echo signals at S-band is investigated in the case of interacting nuclei with a quadrupole moment high enough to cause nuclear quadrupole couplings not negligible with respect to the nuclear Zeeman and dipolar hyperfine couplings. Both the two-pulse and three-pulse electron spin echo envelope modulation (ESEEM) due to²⁷Al and¹⁴N are simulated at different values of the nuclear quadrupole coupling by numerical diagonalization of the nuclear Hamiltonians. The behavior of their amplitude and periods is discussed on the basis of the ratios between the strengths of the nuclear quadrupole interaction and the nuclear Zeeman and the dipolar hyperfine interactions. The interpretation of their trends in terms of the eigenfunctions and eigenvectors of the nuclear Hamiltonians is carried out by using analytical equations obtained by perturbation approaches. First order perturbation treatments for integer and half-integer nuclear spin quantum numbers are developed when the nuclear quadrupole coupling is the main interaction. A discussion on the limits of the interpretation based on the perturbation approach is also given by comparing the magnitude Fourier transform of the patterns calculated by exact diagonalization and analytical equations.     

Comparative analysis of pulsed electron spin resonance spectrometers at X-band and S-band

Comparative analysis of pulsed electron spin resonance spectroscopy at X-band and at S-band indicates that despite the lower sensitivity at the lower frequency, electron spin echo spectroscopy at S-band provides valuable information on the electron-nuclear interactions in systems where the electron spin echo modulation is too small to study well at X-band. It is shown that independent experimental data on electron spin echo modulation and decay at both X-band and S-band put additional constraints on the structural parameters obtained by comparison of experimental and simulated nuclear modulation patterns, and can also help to elucidate the electron spin relaxation mechanism.     

Direct l doublet transitions for the 0110 state of cyanogen iodide

Direct l doublet transitions for the 01¹0 state of ¹²⁷I¹²C¹⁴N and ¹²⁷I¹³C¹⁴N were observed between 4 and 25 GHz using a computer-controlled Stark modulation spectrometer. Values of the l doubling constants and the asymmetry parameters of the ¹²⁷I nuclear quadrupole coupling tensors were derived. Some details of the construction of the spectrometer are also given.     

Pulse EPR spectroscopy of Cu2+-doped inorganic glasses

Two-frequency continuous-wave and pulse EPR (electron paramagnetic resonance) spectroscopical techniques are applied to determine static and dynamic EPR parameters of Cu²⁺ ions in oxide and fluoride glasses. The investigations are focussed on the analysis of strain effects in the glassy matrices, the identification of the magnetic nuclei in the vicinity of Cu²⁺ ions as well as the determination of the dependence of the phase memory timeT _M on temperature and resonance field. The results obtained by X-band continuous-wave EPR, X- and S-band echo-detected EPR, and X- and S-band electron spin echo envelope modulation studies of Cu²⁺-doped inorganic glasses yield information on the local symmetry of the Cu²⁺ coordination polyhedra, the chemical nature of the atoms in the second and higher coordination spheres, the distribution of the parameters of the static spin Hamiltonian and the low-temperature motions of the dopant-containing structural units. Special techniques like 2-D Mims ENDOR (electron nuclear double resonance) and hyperfine-correlated ENDOR are applied for the first time to doped inorganic glasses. From the spin relaxation measurements a stronger tendency of the Cu²⁺ ions to aggregate is found for fluoride glasses in comparison to aluminosilicate and phosphate glasses.     

Microwave spectra of eight isotopic modifications of 1-chloro-1-fluoroethylene

The rotational spectra of eight isotopomers of 1-chloro-1-fluoroethylene in the 6-22 GHz region have been collected and analyzed. Each rotational transition is split into hyperfine components by the chlorine (either ³⁵Cl or ³⁷Cl) nuclear quadrupole coupling interaction and additionally, one or more smaller interactions such as the spin-rotation interaction due to the fluorine atom, hydrogen-hydrogen spin-spin coupling interactions, and in appropriately substituted species, the deuterium nuclear quadrupole hyperfine interaction. The rotational constants derived from these isotopomers allow the determination of average and Kraitchman substitution structures for 1-chloro-1-fluoroethylene, whereas the availability of the diagonal chlorine nuclear quadrupole coupling constants for all the isotopomers provides complete quadrupole coupling tensors for both ³⁵Cl and ³⁷Cl. In the course of this work, the rotational spectrum of an excited vibrational state of the normal isotopomer was observed, which ab initio calculations suggest should be assigned to ν₉=1, an in-plane bending motion at the CFCl end of the molecule.     

Quadrupole moment of the doubly closed shell +1 nucleon nucleus41Sc(Iπ=7/2−)

The nuclear electric quadrupole moment of⁴¹Sc(I^π=7/2⁻) was experimentally determined by use of the NMR detection in which the asymmetric β-ray distribution from spin polarized nuclei was monitored. The magnetic interaction of the state with high external magnetic field and the nuclear quadrupole interaction with the electric field gradient obtained in TiO₂ crystal were studied. The field gradient seen to the implanted⁴¹Sc was measured independently by the high field NMR detection on the stable isotope⁴⁵Sc located in the equivalent⁴¹Sc site with. |Q(⁴¹Sc;I^π=7/2⁻)|=(0.120±0.006) b was determined.     

Elektrische Quadrupolwechselwirkungen von20F im MgF2-Einkristall

Polarized²⁰F nuclei (T _1/2=11s,I=2) have been produced in a tetragonal MgF₂ single crystal by capture of polarized neutrons. Nuclear magnetic resonance transitions have been induced and observed via the asymmetricΒ decay to²⁰Ne, yielding the quadrupole coupling constant ¦e ² q Q/h¦=5.77(2)MHz, the quadrupole moment ¦Q(²⁰F)¦=0.064(12) b and the asymmetry parameter of the electric field gradientη=0.317(2). In order to study possible lattice defects produced by the recoil displacement due to the captureγ-rays NMR signals were registered both at room temperature and at 12 K. Width and depth of the resonance curves indicated that at room temperature nearly all²⁰F ions occupy normal lattice sites with an undisturbed environment. At 12 K, however, where no annealing occurs, this is only true for about half of the²⁰F ions which are stopped directly at defect free sites. The other half of the²⁰F ions at 12 K shows resonance frequencies shifted by defect interactions up to the order of some 100 kHz. Furthermore two simple methods are reported which allow a quick estimate of the strength of the quadrupolar interaction: (1) observation of theΒ decay asymmetry versus the magnetic field strength (decoupling curve), (2) broad-band modulation of the inducedrf field and observation of theΒ asymmetry versus the depth of the modulation.     

Quadrupole interaction of8Li and9Li in LiNbO3 and the quadrupole moment of9Li

The quadrupole interaction of nuclear spin polarized⁸Li (I=2) and⁹Li (I=3/2) in LiNbO₃ has been studied at room temperature. The polarization was achieved by optical pumping of a fast atomic beam with circularly polarized laser light. The atoms were implanted into a hexagonal LiNbO₃ single crystal and the quadrupole splitting ofβ-NMR spectra was measured. A ratio of ¦Q(⁹Li)/Q(⁸Li)¦=0.88(4) for the nuclear quadrupole moments was deduced, yielding a new value of ¦Q(⁹Li)¦=25.3 (9) mb for the quadrupole moment of⁹Li.     

Thermal unpinning of the modulation wave near TI in incommensurate Rb2ZnCl4 detected by 35Cl NQR

Thermal unpinning and floating of the incommensurate modulation wave produces in Rb₂ZnCl₄ close to the incommensurate-paraelectric transition T_I a partial motional averaging of the splitting between the two edge singularities in the ³⁵Cl nuclear quadrupole resonance spectrum. The mean square phase fluctuations are close to T_I proportional to (T_I ? T)^?2β with β = 0.39 ± 0.04.     

Multiple quantum NMR transitions of8Li (T 1/2=0.84 s) in single crystals and powders of LiTaO3, and the quadrupole moment of8Li

Multiple quantum nuclear magnetic resonance (NMR) transitions were observed on polarized⁸Li nuclei, which were produced by capture of polarized neutrons in a single crystal of LiTaO₃. The asymmetric⁸Liβ-radiation distribution was used for the detection of NMR. A quadrupole moment ratio ¦Q(⁸Li)/Q(⁷Li)¦=0.78(1) was determined. Saturation of multiple quantum transitions in nuclear radiation detected NMR may lead to a reduction in measuring time of up to two orders of magnitude, as compared to single quantum detection methods. The measured spectra agree well with an exact lineshape calculation. The same measurements were also performed on a LiTaO₃ powder sample. This was done to test a method to obtain quadrupole coupling constants from high field NMR multiple quantum powder patterns, which are easily detectable, also for higher nuclear spins. This latter method may be applicable also to conventional NMR detection techniques.     

A 236 GHz Fe3+ EPR Study of Nanoparticles of the Ferromagnetic Room-Temperature Semiconductor Sn1−x Fe x O2 (x = 0.005)

High-frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe³⁺ ions at 255 K are reported in a Sn_1?x Fe _x O₂ powder with x = 0.005, which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as the overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe³⁺ ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1) + I(HS2) + I(HS3) + I(HS4)) × exp(?0.00001B), where B is the magnetic field intensity in Gauss, I represents the intensity of an EPR line (HS1, HS2, HS3, HS4), and BL stands for the baseline (the exponential factor, as found by fitting to the experimental spectrum, is related to the Boltzmann population distribution of energy levels at 255 K, which is the temperature of the sample in the spectrometer). These high-frequency EPR results are significantly different from those at X-band. The large values of the zero-field splitting parameter (D) observed here for the four centers at the high frequency of 236 GHz are beyond the capability of X-band, which can only record spectra of ions with much smaller D values than those reported here.     

Mössbauer study of Sn(Fe)O2 prepared by mechanosynthesis

This work deals with first-principles investigation of the electronic structure of the BF₃??H₂O complex which is important in catalysis of organic reactions and polymerization. The dissociation energy of the BF₃??H₂O complex and the nuclear quadrupole interaction parameters for the excited nuclear state ¹⁹F* (I = 5/2) of the fluorine nuclei have been studied. Our investigation shows that the complexation bond BO between the BF₃ and H₂O units is strongly influenced by the larger electronegativity of Oxygen as compared to Nitrogen in BF₃??NH_3. The quadrupole coupling constants of ¹⁹F* and the asymmetry parameter are however quite close to those for BF₃??NH₃. The likely reasons for these features of these two important catalytic systems are suggested.     

Theg-factor of the 9/2+ [624] ground state of183Os

The hyperfine interaction of¹⁸³OsFe has been studied with nuclear magnetic resonance on oriented nuclei after recoil implantation. Taking into account the resonance displacement due to quadrupole interaction |gμ _N H _HF/h|=149.9(2) MHz has been found. WithH _HF=?1,115(20) kG theg-factor of the 9/2⁺ [624] ground state of¹⁸³Os is deduced asg=(?)0.176(3).     

Characteristics of ESEEM and HYSCORE spectra of S>1/2 centers in orientationally disordered systems

One- and two-dimensional electron-spin echo envelope modulation (ESEEM) spectra of Kramers’ multiplets in orientationally disordered systems are simulated using a simple mathematical model. A fairly general high-field spin Hamiltonian is considered with a general g-tensor and arbitrary relative orientations between all tensors involving the electron-spin S, the nuclear spin I, and their interaction. The zero field splitting (ZFS) and the nuclear quadrupole interactions are, however, approximated by their respective secular part in a way that retains all orientation dependencies and it is assumed that the nuclear quadrupole interaction is smaller than the hyperfine interaction. These approximations yield an effective sublevel nuclear Hamiltonian for each EPR transition and are sufficient to account for the most important characteristics of the ESEEM spectra of high electronic multiplets in orientationally disordered systems. Moreover, they allow to obtain some analytical expressions that for I=1/2 illuminate important aspects of 2D hyperfine sublevel correlation (HYSCORE) experiments in S=3/2, 5/2 systems. The pulses are considered as ideal and selective with respect to the different EPR transitions. The contributions of the latter to the echo intensity are weighed according to their different nutation angles and equilibrium Boltzmann populations. For simple axial cases with I=1/2, analytical expressions, analogous to the S=1/2 case, were derived for: (i) the modulation depth, (ii) the lineshapes of the HYSCORE cross-correlation ridges, and (iii) ENDOR powder pattern. Experimental results obtained from Mn(D₂O)₆²⁺ and VO(D₂O)₅²⁺ in frozen solutions are presented, compared, and analyzed in light of the theoretical part.     

Optical orientation of nuclei in nitrogen alloys GaAsN at room temperature

The intensity and giant circular polarization of edge luminescence in a longitudinal magnetic field have been measured in nitrogen alloys GaAsN under circularly polarized pumping. It has been found that these dependences are shifted with respect to zero field by a value B _eff. The magnitude of the internal field B _eff increases with the pumping intensity and reaches saturation (≈250 G) at large excitation densities. The saturation of the B _eff field with growth of pumping indicates that this is a field of nuclei, polarized dynamically due to hyperfine interaction with optically oriented deep paramagnetic centers, rather than a field of exchange interaction created on the center by spin-polarized photo-excited conduction electrons. The short time of nuclear polarization by electrons (<15 μs), measured under modulation of circular polarization of the exciting light with high frequency, points to a small number of nuclei undergoing hyperfine interaction with an electron localized at a center.     

Radio of the nuclear electric quadrupole moments of 50V (I = 6) and 51V (I = 72)

In SmVO₄ the weak paramagnetism of the Sm³⁺ ions results in a very small paramagnetic shift of the vanadium nuclear resonance; the lines are narrow (?4 kHz) and there is no sign of saturation down to 1.7 K. The quadrupole splittings of the two nuclei have been measured at natural abundance in the same single crystal, giving the following value for the ratio of the nuclear electric quadrupole moments: ∥⁵⁰Q/⁵¹Q∥ = 4.07 (3). Values of ⁵¹Q = ?0.0515 (10) b and ⁵⁰Q = +0.209(6) b are suggested.     

Spin-spin interaction of Dy3+ ions in KY(WO4)2

The spin-spin interaction of Dy³⁺ ions in a KY(WO₄)₂ single crystal is investigated by electron paramagnetic resonance (EPR) spectroscopy at a temperature of 4.2 K and a frequency of 9.2 GHz. The EPR spectra of ion pairs located in different coordination shells are analyzed. It is revealed that the considerable contribution to the spin-spin interaction of the nearest neighbor ion pair nn is made not only by the magnetic dipole-dipole interaction but also by the isotropic exchange interaction with the parameter I _nn = (+601 ± 17) × 10^?4cm^?1. The exchange interaction in pairs of more widely spaced ions is substantially weaker: I _5n = (?38 ± 3) × 10^?4cm^?1 and I _9n = (+18 ± 4) × 10^?4cm^?1. For the other ion pairs, the magnetic dipole-dipole interaction dominates. It is found that the EPR spectra of single ions and ion pairs exhibit a superhyperfine structure associated with tungsten nuclei.