Theory of EPR lineshape in samples concentrated in paramagnetic spins: effect of enhanced internal magnetic field on high-field high-frequency (HFHF) EPR lineshape.

A theoretical treatment is provided for the calculation of EPR (electron paramagnetic resonance) lineshape as affected by interactions with paramagnetic ions in the vicinity. The internal fields seen by the various paramagnetic ions due to interactions with paramagnetic ions in their vicinity, as well as the resulting lineshapes, become quite significant at high magnetic fields required in high-frequency (HFHF) EPR. The resulting EPR signals for the various ions are therefore characterized by different g-shifts and lineshapes, so that the overall EPR lineshape, which is an overlap of these, becomes distorted, or even split in HFHF EPR, from that observed at lower frequencies. The observed EPR lineshapes in MnSO(4)⋅H(2)O powder and K(3)CrO(8) single-crystal samples have been simulated here taking into account g-shifts and modified lineshapes. These simulations show that in these samples, concentrated in paramagnetic spins, the position and lineshapes of EPR signals are significantly modified in HFHF EPR involving very high magnetic fields.

A multifrequency EPR study of Fe2+ and Mn2+ ions in a ZnSiF(6).6H2O single crystal at liquid-helium temperatures.

A liquid-helium temperature study of Fe2+ and Mn2+ ions has been carried out on a single crystal of Fe2+-doped ZnSiF(6).6H2O at 5-35K at 170, 222.4 and 333.2G Hz. The spectra are found to be an overlap of two magnetically inequivalent Fe2+ ions, as well as that of an Mn2+ ion. From the simulation of the EPR line positions for the Fe2+ (d6, S=2) ion the spin-Hamiltonian parameters were estimated for the two inequivalent Fe2+ ions at the various temperatures. From the relative intensities of lines the absolute sign of the fine-structure parameters have been estimated. In addition, the fine-structure and hyperfine-structure spin-Hamiltonian parameters for the Mn2+ ion, present as impurity at interstitial sites, were estimated from the hyperfine allowed and forbidden line positions. The particular virtues of such a single-crystal study vs. that on powders are noted.

Calculation of Double-Quantum-Coherence Two-dimensional Spectra: Distance Measurements and Orientational Correlations.

The double quantum coherence (DQC) echo signal for two coupled nitroxides separated by distances ≳10 Å, is calculated rigorously for the six-pulse sequence. Successive application of six pulses on the initial density matrix, with appropriate inter-pulse time evolution and coherence pathway selection leaves only the coherent pathways of interest. The amplitude of the echo signal following the last π pulse can be used to obtain a one-dimensional dipolar spectrum (Pake doublet), and the echo envelope can be used to construct the two-dimensional DQC spectrum. The calculations are carried out using the product space spanned by the two electron-spin magnetic quantum numbers m(1), m(2) and the two nuclear-spin magnetic quantum numbers M(1), M(2), describing e.g. two coupled nitroxides in bilabeled proteins. The density matrix is subjected to a cascade of unitary transformations taking into account dipolar and electron exchange interactions during each pulse and during the evolution in the absence of a pulse. The unitary transformations use the eigensystem of the effective spin-Hamiltonians obtained by numerical matrix diagonalization. Simulations are carried out for a range of dipolar interactions, D, and microwave magnetic field strength B for both fixed and random orientations of the two (14)N (and (15)N) nitroxides. Relaxation effects were not included. Several examples of one- and two-dimensional Fourier transforms of the time domain signals vs. dipolar evolution and spin-echo envelope time variables are shown for illustration. Comparisons are made between 1D rigorous simulations and analytical approximations. The rigorous simulations presented here provide insights into DQC ESR spectroscopy, they serve as a standard to evaluate the results of approximate theories, and they can be employed to plan future DQC experiments.

A 236-GHz Fe EPR STUDY OF NANO-PARTICLES OF THE FERRO-MAGNETIC ROOM-TEMPERATURE SEMICONDUCTOR Sn(1-x)Fe(x)O(2)(x=0.005).

High frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe(3+) ions at 255 K are reported in a Sn(1-x)Fe(x)O(2) powder with x = 0.005 which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe(3+) ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1)+I(HS2)+I(HS3)+I(HS4))×e(-0.00001×B), 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 base line. (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 only with much smaller D values than those reported here.

Simulation of slow-motion CW EPR spectrum using stochastic Liouville equation for an electron spin coupled to two nuclei with arbitrary spins: matrix elements of the Liouville superoperator.

An algorithm is developed that extends the well known nitroxide slow-motional continuous wave electron paramagnetic resonance (EPR) simulation technique developed originally by Meirovitch et al. [E. Meirovitch, D. Inger, E. Inger, G. Moro, J.H. Freed, J. Chem. Phys. 77 (1982) 3915-3938], and implemented by Schneider and Freed [D.J. Schneider, J.H. Freed, Calculating slow motional magnetic resonance spectra: a user's guide, in: Biological Magnetic Resonance, vol. 6, Plenum Publishing Corporation, 1989]. This paper deals with the more general case of coupling of one electron spin to two nuclear spins. A complete listing of the matrix elements of the Liouville superoperator for this extension has been included. This advance has been successfully tested by reproducing the observed spectral lineshapes of a solution of the novel radical Mes(*)(CH(3))P-PMes(*) [Mes(*)=2,4,6 (tBu)(3)C(2)H(2)] in tetrahydrofuran (THF), in which the radical is undergoing slow tumbling, with the coupling of one electron spin to two physically and magnetically inequivalent phosphorus ((31)P) nuclei.

Exchange-mediated spin-lattice relaxation of Fe3+ ions in borate glasses.

Spin-lattice relaxation times (T1) of two borate glasses doped with different concentrations of Fe2O3 were measured using the Electron Spin-Echo (ESE) technique at X-band (9.630 GHz) in the temperature range 2-6K. In comparison with a previous investigation of Fe3+-doped silicate glasses, the relaxation rates were comparable and differed by no more than a factor of two. The data presented here extend those previously reported for borate glasses in the 10-250K range but measured using the amplitude-modulation technique. The T1 values were found to depend on temperature (T) as T(n) with n approximately 1 for the 1% and 0.1% Fe2O3-doped glass samples. These results are consistent with spin-lattice relaxation as effected by exchange interaction of a Fe3+ spin exchange-coupled to another Fe3+ spin in an amorphous material.

A variable temperature EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 170 GHz: zero-field splitting parameter and its absolute sign.

EPR measurements have been carried out on a single crystal of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) at 170-GHz in the temperature range of 312-4.2K. The spectra have been analyzed (i) to estimate the spin-Hamiltonian parameters; (ii) to study the temperature variation of the zero-field splitting (ZFS) parameter; (iii) to confirm the negative absolute sign of the ZFS parameter unequivocally from the temperature-dependent relative intensities of hyperfine sextets at temperatures below 10K; and (iv) to detect the occurrence of a structural phase transition at 4.35K from the change in the structure of the EPR lines with temperature below 10K.

Using the diphosphanyl radical as a potential spin label: effect of motion on the EPR spectrum of an R1(R2)P--PR1 radical.

The EPR spectrum of the novel radical Mes*(CH3)P--PMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the P--P bond.

Variable-frequency EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 9.6, 36, and 249.9 GHz: structural phase transition.

Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures.