Observation of potassium hyperfine interactions in x-irradiated KH2AsO4 through the method of electron spin echo envelope modulation

Hyperfine interaction frequencies of ¹H and ³⁹K nuclei near the AsO^4-₄ radical in X-ray irradiated KH₂AsO₄ (KDA) have been observed through the method of electron spin echo envelope modulation (ESEEM). This method enabled us to record nuclear hyperfine interaction (ENDOR-like) spectra around the ferroelectric phase transition of KDA for the first time. The ESEEM spectrum of ³⁹K exhibits a clear change when passing the ferroelectric phase transition temperature, but that of close protons does not. The result for close protons is in agreement with the symmetry breaking of the AsO^4-₄ site as observed via the EPR spectrum [5]. Finally, at 4.2 K the hyperfine interaction parameters of a ³⁹K nucleus near the AsO^4-₄ unit could be determined through the ESEEM method.     

Line-shifting method in electron spin echo envelope modulation (ESEEM) studies

A novel line-shifting method, which is called mixing-frequency electron spin echo envelope modulation (MIF-ESEEM) spectroscopy, is introduced and analysed. It is shown that the spectral resolution is enhanced, and thus the overlapping is removed with this new method. The application of this method to systems withS≥1 andI≥1 is also discussed.     

Analysis of anisotropic hyperfine interaction distributions in two-dimensional four- and five-pulse electron spin echo envelope modulation spectra of protons in single crystals

The effect of the distribution of anisotropic hyperfine interaction on the cross peak line shape of protons in single crystal two-dimensional four-pulse electron spin echo envelope modulation spectra are discussed. The inclusion of an additional mixing pulse in the evolution period of the four-pulse sequence allows the simultaneous measurement of cross and sum peaks in a two-dimensional experiment. The sum peaks directly map the distribution of the anisotropic hyperfine interaction. As an experimental example the hyperfine interaction parameter distribution of protons localzed in hydrogen bonds of a mixed single crystal betaine phosphate/betaine phosphite is examined.     

Refocused primary echo: A zero dead time detection of the electron spin echo envelope modulation

We report on the two-dimensional (2D) implementation of the refocused primary electron spin echo envelope modulation (ESEEM) technique, its theory and experimental application to a model system and a system of biological interest. This technique is virtually free of dead time along one time coordinate. The ESEEM obtained by integration of the 2D time-domain data of the refocused primary ESEEM over one of the time coordinates shows the intensity of the sum combination harmonics proportional to k² for k 1 and proportional to k for k 1 (k is a usual notation for the modulation amplitude factor). This feature, in combination with the adjustment of k by means of variation of the operational frequency of the spectrometer, was found to be very useful for detection of protons with distributed hyperfine interaction parameters situated close to the electron spin.     

5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems

In 3-pulse ESEEM and the original 4-pulse HYSCORE, nuclei with large modulation depth (k approximately 1) suppress spectral peaks from nuclei with weak modulations (k approximately 0). This cross suppression can impede the detection of the latter nuclei, which are often the ones of interest. We show that two extended pulse sequences, 5-pulse ESEEM and 6-pulse HYSCORE, can be used as experimental alternatives that suffer less strongly from the cross suppression and allow to recover signals of k approximately 0 nuclei in the presence of k approximately 1 nuclei. In the extended sequences, modulations from k approximately 0 nuclei are strongly enhanced. In addition, multi-quantum transitions are absent which simplifies the spectra. General analytical expressions for the modulation signals in these sequences are derived and discussed. Numerical simulations and experimental spectra that demonstrate the higher sensitivity of the extended pulse sequences are presented.     

Determination of the deuterium content of deuterated betaine arsenate by electron spin echo envelope modulation

An alternative method for the determination of the deuterium content in the hydrogen bonds of ferroelectric/antiferroelectric deuterated betaine arsenate is presented. Carbon radicals formed by gamma irradiation of the betaine arsenate have been used as paramagnetic probes. The deuterium content in the hydrogen bonds has been determined by analyzing the modulation in the electron spin echo spectra of the carbon radical (CH₃)₃N+CHCOO^? which arises because of the dipolar interactions between the paramagnetic radical and the deuterium nuclei.     

Dynamic nuclear polarization in electron spin echo

It is shown that under the action of a proper microwave pulse sequence the equilibrium polarization of the electron spin may be transferred dynamically to the longitudinal nuclear magnetization which will oscillate due to the nuclear spin precession around the effective fields relating to differnt electron quantum number manifolds. These oscillations may be measured directly in the radiofrequency band. Analytical formulae are obtained for the case when all the nuclei coupled to an unpaired electron have spins of 1/2.     

Theory of knight shift due to indirect nuclear hyperfine interactions

We derive a theory of Knight shift (K) in solids including the effects of periodic potential, spin-orbit interaction, magnetic hyperfine interactions and indirect nuclear hyperfine interaction. We use a temperature dependent Green's function technique to evaluate the thermodynamic potential which is then used to obtain a general expresion for the Knight shift. Our formula for K is expressed as a sum of contributions due to conduction electrons and localized electrons of either d- or f-type: K_cond and K_loc. While K_cond is the same as our previous expression for K derived in the absence of localized magnetic moments, K_loc is a new contribution and is due to the hybridization of conduction and localized electron magnetic moments. We also briefly discuss the many-body effects on the different contributions to K. Finally, the importance of the present theory in possible applications to metals, alloys and compounds containing transition and rare-earth elements, and magnetic semiconductors is discussed.     

Pure absorption electron spin echo envelope modulation spectra by using the filter-diagonalization method for harmonic inversion

Harmonic inversion of electron spin echo envelope (ESEEM) time-domain signals by filter diagonalization is investigated as an alternative to Fourier transformation. It is demonstrated that this method features enhanced resolution compared to Fourier-transform magnitude spectra, since it can eliminate dispersive contributions to the line shape, even if no linear phase correction is possible. Furthermore, instrumental artifacts can be easily removed from the spectra if they are narrow either in time or frequency domain. This applies to echo crossings that are only incompletely eliminated by phase cycling and to spurious spectrometer frequencies, respectively. The method is computationally efficient and numerically stable and does not require extensive parameter adjustments or advance knowledge of the number of spectral lines. Experiments on gamma-irradiated methyl-alpha-d-glucopyranoside show that more information can be obtained from typical ESEEM time-domain signals by filter-diagonalization than by Fourier transformation.     

A comment on the theory of one-dimensional mixing-frequency electron spin echo envelope modulation (MIF-ESEEM) spectroscopy

The theory of one-dimensional mixing-frequency electron-spin-echo envelope modulation (MIF-ESEEM) spectroscopy of disordered systems has been revised. In particular, the correct dependence of the position and width of the MIF-ESEEM peaks on the experimental parameters has been obtained, thus providing formulas which enable one to properly interpret the experimental data. The differences with the previously published analyses are discussed. The close relationship with the two-dimensional HYSCORE spectroscopy is remarked on. Experimental examples demostrate the main results.     

Electron spin resonance and electron spin echo modulation studies of Fe-containing mesoporous MCM-48 molecular sieves

Through electron spin resonance (ESR) and electron spin echo modulation (ESEM) studies, three Fe(III) species are found in liquid ion-exchanged Fe-MCM-48 and synthesized FeMCM-48. Species A with ESR parameters g^A = 4.30 with a line width of 160 G is observed in hydrated samples. This species is accompanied by a shoulder atg = 7.60 and is assigned to distorted tetrahedral Fe(III) likely located at framework defect sites. Species B is a broad peak centered at g^B = 2.00 and is assigned to distorted octahedral Fe(III) located at extraframework sites. This species is also observed in dehydrated samples. Species C is a very narrow isotropic signal at g^C = 4.30 with a line width of 30 G and is only observed in synthesized mesophase materials. It is consistent with rhombic Fe(III) with zero field parametersD andE corresponding toD/E =1/3 and is assigned to tetrahedral Fe(III) located at framework sites. Framework Fe(III) in FeMCM-48 is less accessible to ND₃ than is extraframework Fe(III) in Fe-MCM-48. On the basis of deuterium ESEM data, framework Fe(III) in synthesized FeMCM-48 directly coordinates to two D₂O or CH₃OD molecules and interacts more weakly with two more molecules. However, no deuterium ESEM is observed for extraframework Fe(III) in ion-exchanged Fe-MCM-48 with adsorbed D₂O or CH₃OD. It is also found that Fe(III) is incorporated into the framework of FeMCM-48 at an early stage of the formation of the MCM-48 mesostructure.     

Modulation effects in the electron spin echo resulting from hyperfine interaction with a nucleus of an arbitrary spin

Exact analytic expressions for the modulation effects in two- and three-pulse electron spin echoes resulting from the hyperfine interaction of an electron and a nucleus with an arbitrary spin are derived. The two-pulse envelope modulation is calculated numerically for some nuclei for which modulation effects are most often observed experimentally. Applicability requirements of the conventional approximate formula for analysis of the ESE modulation effects are considered.     

Recovery of broad hyperfine lines in electron spin-echo envelope modulation spectroscopy of disordered systems

A novel approach is proposed for the recording and processing of electron spin-echo envelope modulation spectra that is less sensitive to lineshape distortions of broad hyperfine lines. An unusually long pulse delay is employed in three-pulse stimulated-echo experiments. Observation is restricted to the so-called echo-modulation echo, and magnitude calculation is used to eliminate blind spots that distort conventional three-pulse echo-modulation spectra.     

Suppression of electron spin-echo envelope modulation peaks in double quantum coherence electron spin resonance

We show the use of the observer blind spots effect for the elimination of electron spin-echo envelope modulation (ESEEM) peaks in double quantum coherence (DQC) electron spin resonance (ESR). The suppression of ESEEM facilitates the routine and unambiguous extraction of distances from DQC-ESR spectra. This is also the first demonstration of this challenging methodology on commercial instrumentation.     

Electric field tunability of nuclear and electronic spin dynamics due to the hyperfine interaction in semiconductor nanostructures

We present formulas for the nuclear and electronic spin relaxation times due to the hyperfine interaction for nanostructed systems and show that the times depend on the square of the local density of electronic states at the nuclear position. A drastic sensitivity (orders of magnitude) of the electronic and nuclear spin coherence times to small electric fields is predicted for both uniformly distributed nuclear spins and delta-doped layers of specific nuclei. This sensitivity is robust to nuclear spin diffusion.     

Phase modulation of recoilless gamma radiation by nuclear zeeman effect

The use of an alternating magnetic field for phase modulation of recoilless gamma radiation is studied. The measurements were performed with the Mössbauer resonances of Fe-57 and Zn-67. Novel time-domain data are presented from experiments on the nuclear Zeeman effect at high modulation frequencies.     

Electron spin echo modulation and relaxation in polythiophene

Electron spin echo measurements on neutral poly (thiophene) show a clear modulation of the spin-echo decay. Analysis of the modulation and its Fourier transformed (ω) power spectrum indicates that the wave function of the spin defect is extended over ～ 25 proton nuclei. The functional behavior of the longitudinal relaxation, T₁, versus temperature is very similar to that observed previously for (CH)_x, although T₁ values for poly (thiophene) are significantly longer.     

Nuclear spin echo in magnetics with inhomogeneous hyperfine and quadrupole interaction

Additional spin-ocho signale from quadrupole nuclei with I=7/2 (Co⁵⁹ nuclei in Co and Fe−Co thin films) were investigated. It has been shown, that the time dependence of the additional ocho signals, arising at the time moments 2nς reflect quadrupole interaction inhomogenety.     

Anisotropic hyperfine interactions and spin relaxation in neptunyl salts

Mössbauer spectra of hexavalent neptunyls X₂(NpO₂)Cl₄ and X₄(NpO₂)(CO₃)₃ with X=Na, K, Cs, (NH₄) and [C₂H₅)₄N] are discussed and compared to EPR data. In cases where reliable values of hyperfine parameters can be extracted, the Mössbauer spectra give fine details of bonding structure. It is found that the O–Np–O bond is not linear and that exchanging the cation results in small but definite changes.Work supported by the Bundesministerium für Forschung und Technologie and the U.S. Department of Energydeceased