Hyperfine Tensors Research Articles

Computational study of electron paramagnetic resonance parameters for Mg and Zn impurities in β -Ga2O3

A computational study of electron paramagnetic resonance (EPR) g-tensors and hyperfine tensors in Mg- and Zn-doped β-Ga2O3 is presented. While Mg has been found previously to prefer the octahedral site, we find here that Zn prefers the tetrahedral substitutional site. The EPR signatures are found to be distinct for the two sites. Good agreement with experiment is found for the g-tensor and the hyperfine interaction for MgGa2, and predictions are made for the Zn case.

All-electron density functional calculations for electron and nuclear spin interactions in molecules and solids

The interaction between electronic and nuclear spins in the presence of external magnetic fields can be described by a spin Hamiltonian, with parameters obtained from first principles, electronic structure calculations. We describe an approach to compute these parameters, applicable to both molecules and solids, which is based on Density Functional Theory (DFT) and real-space, all-electron calculations using finite elements (FE). We report results for hyperfine tensors, zero field splitting tensors (spin-spin component) and nuclear quadrupole tensors of a series of molecules and of the nitrogen-vacancy center in diamond. We compare our results with those of calculations using Gaussian orbitals and plane-wave basis sets, and we discuss their numerical accuracy. We show that calculations based on FE can be systematically converged with respect to the basis set, thus allowing one to establish reference values for the spin Hamiltonian parameters, at a given level of DFT.

Vanadium in yttrium aluminum garnet: Charge states and localization in the lattice

Incorporation of the V3+ and V4+ ions into the yttrium aluminum garnet Y3Al5O12 (YAG) lattice has been studied by the correlated optical absorption and electron paramagnetic resonance (EPR) measurements. Only the V3+ ions at both octahedral and tetrahedral aluminum sites are found in as-grown crystals. However, annealing in air leads to the transformation of the V3+ to V4+, whereas annealing in the hydrogen atmosphere remains the V3+ concentration almost unchanged. Spin Hamiltonian parameters of the V3+ and V4+ ions at the tetrahedral sites including the zero field splitting and 51V hyperfine constants are determined using high-frequency, up to 300 GHz, EPR measurements. By using the spin Hamiltonian parameters, the ground state energy levels splitting of the V3+ and V4+ ions were calculated in the framework of the crystal field theory. The g and hyperfine tensors suggest that electron density around the tetrahedral V3+ ion is distributed strongly inhomogeneously resulting also in large (40%) reduction of the spin-orbit coupling constant whereas the tetrahedral V4+ ion exhibits weaker covalent bounding with surrounding ligands. Furthermore, the obtained EPR data on vanadium ions allow to improve identification of the optical absorption peaks in YAG:V crystals.

Identification of divacancy and silicon vacancy qubits in 6H-SiC

Point defects in semiconductors are relevant for use in quantum technologies as room temperature qubits and single photon emitters. Among suggested defects for these applications are the negatively charged silicon vacancy and the neutral divacancy in SiC. The possible nonequivalent configurations of these defects have been identified in 4H-SiC, but for 6H-SiC, the work is still in progress. In this paper, we identify the different configurations of the silicon vacancy and the divacancy defects to each of the V1-V3 and the QL1-QL6 color centers in 6H-SiC, respectively. We accomplish this by comparing the results from ab initio calculations with experimental measurements for the zero-phonon line, hyperfine tensor, and zero-field splitting.

Single-Crystal Study of a Low Spin Co(II) Molecular Qubit: Observation of Anisotropic Rabi Cycles.

A mononuclear low spin ( S = 1/2) Co(II) molecule crystallized in a 4-fold symmetry is fully investigated by CW and pulsed EPR on a single crystal sample. The quantum phase memory time of the molecule around 1 μs at 5 K is direction-independent, while the Rabi oscillation frequency is anisotropic. The spin Hamiltonian analyses reveal that the anisotropic Landé factor and hyperfine tensor do not influence the anisotropy apparently when the microwave magnetic field is applied along a certain direction. It is considered that the possibly involved nuclear spin forbidden transitions may be responsible for the small distinction of Rabi frequencies in two directions.

Hyperfine tensors for a model system for the oxygen evolving complex of photosystem II: calculation of the anisotropy shift that occurs beyond the strong exchange limit.

Broken-symmetry density functional calculations have been used to calculate effective 55Mn hyperfine (A) tensors for a mixed-valence tetranuclear manganese complex, a model system for the S2 state of the oxygen-evolving complex of photosystem II. Recent investigations carried out in our laboratory showed that for calculations within the strong exchange limit, density functional calculations cannot reproduce the relative magnitude of the anisotropy of the hyperfine tensors of the MnIII center compared to the MnIV centers. In this work we therefore go beyond the strong exchange limit and investigate the effect of multiplet mixing, induced by zero-field splitting, on the effective hyperfine tensors through a perturbational treatment within the numerical spin projection procedure. Results show that the inclusion of zero-field splitting leads to a shift of the anisotropy from the MnIII ion towards the three MnIV ions, thus reconciling the calculated and experimentally observed anisotropy pattern. However, the final results are quite sensitive to the energy gap between the ground (doublet) and the first excited (quartet) state and therefore critically depend on the appropriate choice of the isotropic exchange coupling constants.

Spectroscopic study of hyperfine properties in Yb3+171:Y2SiO5

Rare-earth ion-doped crystals are promising systems for quantum communication and quantum information processing. In particular, paramagnetic rare-earth centers can be utilized to realize quantum coherent interfaces simultaneously for optical and microwave photons. In this paper, we study hyperfine and magnetic properties of a ${\mathrm{Y}}_{2}{\mathrm{SiO}}_{5}$ crystal doped with $^{171}\mathrm{Yb}^{3+}$ ions. This isotope is particularly interesting since it is the only rare--earth ion having electronic spin $S=\frac{1}{2}$ and nuclear spin $I=\frac{1}{2}$, which results in the simplest possible hyperfine level structure. In this work, we determine the hyperfine tensors for the ground and excited states on the optical $^{2}\mathrm{F}_{7/2}(0)\ensuremath{\longleftrightarrow}^{2}\mathrm{F}_{5/2}(0)$ transition by combining spectral hole burning and optically detected magnetic resonance techniques. The resulting spin Hamiltonians correctly predict the magnetic-field dependence of all observed optical-hyperfine transitions, from zero applied field up to fields where the Zeeman interaction is dominating the hyperfine interaction. Using the optical absorption spectrum, we can also determine the order of the hyperfine levels in both states. These results pave the way for realizing solid-state optical and microwave quantum memories based on a $^{171}\mathrm{Yb}^{3+}:{\mathrm{Y}}_{2}{\mathrm{SiO}}_{5}$ crystal.

Theoretical confirmation of the polaron model for the Mg acceptor in β-Ga2O3

β-Ga2O3 has recently been considered for power electronics applications but p-type doping is an issue, especially since small hole polarons were predicted and observed in this material. Recently, by using a gap-optimized, Koopmans-compliant hybrid functional, we were able to reproduce the observed charge transition levels of defects, including the hole polaron in the intrinsic material. In this study, the same hybrid functional is used to confirm the assignment of the electron paramagnetic resonance (EPR) spectrum observed in Mg-doped β-Ga2O3 samples. The Mg impurity introduces a deep acceptor level in β-Ga2O3 corresponding to a small polaron, localized at an oxygen site adjacent to the substitutional Mg. The so-called O1 site is energetically favored and the superhyperfine interactions with the neighboring tetrahedrally coordinated Ga atom are 1.9 times stronger than with the neighboring octahedrally coordinated Ga. The calculated hyperfine tensor agrees well with the EPR measurement. These results confirm that Mg cannot act as a shallow acceptor in β-Ga2O3.

Charge trapping processes and energy transfer studied in lead molybdate by EPR and TSL

Charge trapping and energy transfer processes are investigated in PbMoO4 single crystals by electron paramagnetic resonance (EPR) and wavelength-resolved thermally stimulated luminescence (TSL) in a correlated manner. New signals produced by two differently perturbed Mo5+ centers (Mo2 and Mo3) were observed in EPR spectra measured in the crystals after 420 nm light irradiation. Two sets of spin-Hamiltonian parameters, g tensor and the 95,97Mo, 207Pb (super) hyperfine tensors, have been determined and analyzed in terms of crystal field and LCAO-MO theories. A significant overlap of the Mo 5d1 and 6s6p ligand Pb orbitals was deduced for the Mo3 whereas the Mo2 center seemed to be not or very slightly affected by the lead orbitals. The obtained TSL results allowed to suppose the existence of at least six glow peaks produced by the de-trapping of charge carrier traps either of intrinsic nature or somehow stabilized by nearby accidental impurities. The peaks having maxima at 51 K, 79 K, and 89 K, in particular, were attributed to the Mo2 and Mo3 centers thermal destruction due to the observed correspondence between the kinetic parameters (trap depths and frequency factors) determined separately for the glow peaks and the EPR intensity thermal decay curves of these centers. The Mo2 EPR decay curve is rather complex experiencing two-step trend probably due to trapped electron recombination with some holes released below 60 K. It was further confirmed by the TSL emission maximum relatively large red shift (~ 100 nm) compared to the much smaller offset measured in radioluminescence. This phenomenon, observed also in samples obtained from extra-pure starting materials, was explained by three-component origin of the spectra, each having its own thermal fading rate. One of them ceased to exist above 60 K. The discussion of the obtained results is provided in comparison with other representatives of the scheelite tungstate and molybdate-based single crystals.

Broken Symmetry Approach to Magnetic Properties of Oligonuclear Transition-Metal Complexes: Application to Hyperfine Tensors of Mixed-Valence Manganese Compounds

The broken symmetry method is a standard approach for the calculation of isotropic exchange coupling constants in oligonuclear transition-metal compounds with density functional methods. It is most...

Probing Axial Water Bound to Copper in Tutton Salt Using Single Crystal 17O-ESEEM Spectroscopy.

Electron spin-echo envelope modulation (ESEEM) signals attributed to axial water bound to Cu2+ have been detected and analyzed in Cu(II)-doped 17O-water-enriched potassium zinc sulfate hexahydrate (Tutton salt) crystals. The magnetic field orientation dependences of low frequency modulations were measured to fit hyperfine and quadrupole coupling tensors of a 17O ( I = 5/2) nucleus. The hyperfine tensor ( A xx, A yy, A zz: 0.13, 0.23, -3.81 MHz) exhibits almost axial symmetry with the largest value directed normal to the metal equatorial plane in the host structure. Comparisons with quantum chemical calculations position this nucleus about 2.3 Å from the copper. The isotropic coupling (-1.15 MHz) is small and reflects the weak axial water interaction with a dx2-y2 unshared orbital of copper. The 17O-water quadrupole interaction parameters ( e2 qQ/ h = 6.4 MHz and η = 0.93) are close to the average of those found in a variety of solid hydrates. In addition, the coupling tensor directions correlate very closely with the O8 water geometry, with the maximum quadrupole direction 3° from the water plane normal, and its minimum coupling about 2° from the H-H direction. In almost all previous magnetic resonance 17O-water studies, the quadrupole tensor orientation was based on theoretical considerations. This work represents one of the few experimental confirmations of its principal axis frame. When Cu2+ dopes into the Tutton salt, a Jahn-Teller distortion interchanges the relative long and intermediate metal O7 and O8 bond lengths of the zinc host. Therefore, only those unit cells containing the impurity conform to the pure copper Tutton structure. This study provides further support for this model. Moreover, coupling interactions from distant H217O such as in the present case have important implications in studies of copper enzymes and proteins where substrates have been proposed to displace weakly bound water in the active site.

G-Tensor Directions in the Protein Structural Frame of Hyperthermophilic Archaeal Reduced Rieske-Type Ferredoxin Explored by 13C Pulsed Electron Paramagnetic Resonance.

Interpretation of magnetic resonance data in the context of structural and chemical biology requires prior knowledge of the g-tensor directions for paramagnetic metallo-cofactors with respect to the protein structural frame. Access to this information is often limited by the strict requirement of suitable protein crystals for single-crystal electron paramagnetic resonance (EPR) measurements or the reliance on protons (with ambiguous locations in crystal structures) near the paramagnetic metal site. Here we develop a novel pulsed EPR approach with selective 13Cβ-cysteine labeling of model [2Fe-2S] proteins to help bypass these problems. Analysis of the 13Cβ-cysteine hyperfine tensors reproduces the g-tensor of the Pseudomonas putida ISC-like [2Fe-2S] ferredoxin (FdxB). Its application to the hyperthermophilic archaeal Rieske-type [2Fe-2S] ferredoxin (ARF) from Sulfolobus solfataricus, for which the single-crystal EPR approach was not feasible, supports the best-fit g x-, g z-, and g y-tensor directions of the reduced cluster as nearly along Fe-Fe, S-S, and the cluster plane normal, respectively. These approximate principal directions of the reduced ARF g-tensor, explored by 13C pulsed EPR, are less skewed from the cluster molecular axes and are largely consistent with those previously determined by single-crystal EPR for the cytochrome bc1-associated, reduced Rieske [2Fe-2S] center. This suggests the approximate g-tensor directions are conserved across the phylogenetically and functionally divergent Rieske-type [2Fe-2S] proteins.

<i>Ab Initio</i> Theory of Si-Vacancy Quantum Bits in 4H and 6H-SiC

Point defects in wide band gap semiconductors have recently shown outstanding potential for implementing room temperature quantum bits and single photon emitters. These atomic scale tools can be used in various quantum information processing, sensing, and imaging applications. Silicon vacancy related photoluminescence centers in 4H, 6H, and 15R-SiC are among the most studied quantum bits that possess a particular spin-3/2 ground and excited state. The microscopic structures of these defects have been recently identified as isolated negatively charged silicon vacancy defects at the symmetrically non-equivalent silicon sites in SiC. Relying on this identification, here we carry out high precision ab initio simulations on negatively charged silicon vacancies in 4H and 6H-SiC and calculate the most important magneto-optical data, such as the zero-phonon photoluminescence energies, the zero-field-splitting, and the hyperfine tensors for the nearest and farther nuclear spins.

Estimation of vector static magnetic field by a nitrogen-vacancy center with a single first-shell 13C nuclear (NV–13C) spin in diamond**Protect supported by the National Natural Science Foundation of China (Grant Nos. 11305074, 11135002, and 11275083), the Key Program of the Education Department Outstanding Youth Foundation of Anhui Province, China (Grant No. gxyqZD2017080), and the Natural Science Foundation of Anhui Province,

We suggest an experimental scheme that a single nitrogen-vacancy (NV) center coupled to a nearest neighbor 13C nucleus as a sensor in diamond can be used to detect a static vector magnetic field. By means of optical detection magnetic resonance (ODMR) technique, both the strength and the direction of the vector field could be determined by relevant resonance frequencies of continuous wave (CW) and Ramsey spectrums. In addition, we give a method that determines the unique one of eight possible hyperfine tensors for an (NV–13C) system. Finally, we propose an unambiguous method to exclude the symmetrical solution from eight possible vector fields, which correspond to nearly identical resonance frequencies due to their mirror symmetry about 14N–Vacancy–13C (14N–V–13C) plane.

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO4 and LiCoPO4.

A novel protocol to compute and analyze NMR chemical shifts for extended paramagnetic solids, accounting comprehensively for Fermi-contact (FC), pseudocontact (PC), and orbital shifts, is reported and applied to the important lithium ion battery cathode materials LiFePO4 and LiCoPO4. Using an EPR-parameter-based ansatz, the approach combines periodic (hybrid) DFT computation of hyperfine and orbital-shielding tensors with an incremental cluster model for g- and zero-field-splitting (ZFS) D-tensors. The cluster model allows the use of advanced multireference wave function methods (such as CASSCF or NEVPT2). Application of this protocol shows that the 7Li shifts in the high-voltage cathode material LiCoPO4 are dominated by spin-orbit-induced PC contributions, in contrast with previous assumptions, fundamentally changing interpretations of the shifts in terms of covalency. PC contributions are smaller for the 7Li shifts of the related LiFePO4, where FC and orbital shifts dominate. The 31P shifts of both materials finally are almost pure FC shifts. Nevertheless, large ZFS contributions can give rise to non-Curie temperature dependences for both 7Li and 31P shifts.

Pulse EPR and ENDOR Study of Manganese Doped [(CH3)2NH2][Zn(HCOO)3] Hybrid Perovskite Framework

We present a pulse electron paramagnetic resonance (EPR) and electron–nuclear double resonance (ENDOR) study of a manganese-doped [(CH3)2NH2][Zn(HCOO)3] dense metal–organic framework which exhibits a structural phase transition at 163 K. The echo-detected field sweep Mn2+ EPR spectrum of the low-temperature phase is in a perfect agreement with the previous continuous-wave EPR results, while the spectrum of the disordered phase reveals a significant EPR transition-dependent relaxation. The 1H ENDOR pattern indicates several protons in the vicinity of the Mn2+ ion. The experimental ENDOR spectrum is successfully simulated using the proton hyperfine tensors calculated by the density functional theory. A multifrequency electron spin echo envelope modulation (ESEEM) spectroscopy shows a peculiar signal which is unaffected by the external magnetic field. The modulation depth of this signal starts to decrease above 40 K, coinciding with the temperature at which the methyl groups of the (CH3)2NH2+ cations start t...

Determination of the Complete Spin Density Distribution in 13C-Labeled Protein-Bound Radical Intermediates Using Advanced 2D Electron Paramagnetic Resonance Spectroscopy and Density Functional Theory.

Determining the complete electron spin density distribution for protein-bound radicals, even with advanced pulsed electron paramagnetic resonance (EPR) methods, is a formidable task. Here we present a strategy to overcome this problem combining multifrequency HYSCORE and ENDOR measurements on site-specifically 13C-labeled samples with DFT calculations on model systems. As a demonstration of this approach, pulsed EPR experiments are performed on the primary QA and secondary QB ubisemiquinones of the photosynthetic reaction center from Rhodobacter sphaeroides 13C-labeled at the ring and tail positions. Despite the large number of nuclei interacting with the unpaired electron in these samples, two-dimensional X- and Q-band HYSCORE and orientation selective Q-band ENDOR resolve and allow for a characterization of the eight expected 13C resonances from significantly different hyperfine tensors for both semiquinones. From these results we construct, for the first time, the most complete experimentally determined maps of the s- and pπ-orbital spin density distributions for any protein organic cofactor radical to date. This work lays a foundation for understanding the relationship between the electronic structure of semiquinones and their functional properties, and introduces new techniques for mapping out the spin density distribution that are readily applicable to other systems.

Electron self-trapped at molybdenum complex in lead molybdate: An EPR and TSL comparative study

Single crystals of PbMoO4 were studied by means of light-induced electron paramagnetic resonance (EPR) and wavelength resolved thermally stimulated luminescence (TSL). The work is focused on the electron self-trapped at the (MoO4)2- complex. Detailed analysis of the EPR spectra of this complex allowed to determine a set of spin-Hamiltonian parameters including g factor and the 95,97Mo, 207Pb hyperfine tensors further used in calculations performed in terms of crystal field and LCAO-MO theories. They have shown a significant overlap of the Mo 5d1 and 6s6p ligand lead orbitals. The contributions of oxygen and lead to the molecular orbitals with an electron trapped at the (MoO4)3- complex were about 14% and 38%, respectively. The decay of the molybdenum center EPR intensity with annealing temperature provided information about thermal stability of the center, which thermally destroys already at 40K. Trap depth and frequency factor, Et = 0.05eV, and f0 = 104s−1, have been determined. The TSL glow curve displays two overlapping peaks in the 40–50K temperature region, corresponding to the disappearance of the EPR signal from the (MoO4)3- center. By partial cleaning technique and initial rise method it is shown that the lower temperature peak is related to a trap with thermal parameters similar to those determined for the (MoO4)3- center. This allows to correlate it to the thermal destruction of the (MoO4)3- center. The obtained results are discussed in a broader frame of charge trapping mechanism in all the family of tungstate and molybdate-based single crystals.

Comparison of nitrogen-vacancy complexes in diamond and cubic SiC: dose dependencies and spin-Hamiltonian parameters

At present the nitrogen-vacancy (NV) complex in diamond is the most promising defect for application in the area of quantum computing. This provides a stimulus for an extensive search of other defects in semiconductors with similar properties. Recently it was shown that the NCVSi defect complex in SiC is perspectively appropriate for this goal as well. In the present work we perform comparative ab initio studies of NV complexes in diamond and 3C-SiC. We focus both on radiospectroscopic characterization of these defects and on the calculation of the equilibrium concentration of complexes in irradiated crystals. In particular a full set of spin-Hamiltonian parameters including g-tensors, hyperfine tensors and the spin–spin part of zero-field splitting constant Dss were calculated for both negative and neutral charge states as well as for excited quartet states of neutral complexes. Comparison of calculated values with the available experimental data and results of other calculations show good agreement, especially in the case when hybrid and meta-hybrid functionals were used. This makes the unambiguous identification of negative NV complexes in both materials possible. Our calculations reveal that the ground states of neutral complexes are a difficult case for both DFT calculations and experimental observations. This is caused by multi-determinantal behavior of wave function for such complexes, which leads to a large amount of spin contamination and to the broken symmetry solution which appeared for single Slater determinant DFT calculations. Based on the calculated minimum of free energy of neutral and negative complexes in SiC and diamond we obtained the equilibrium concentrations of these complexes depending on the vacancy concentration produced by irradiation. We show that in some dose regions both negative and neutral complexes coexist, while in other regions only one charge state prevails. Comparison of the calculated and experimental dose dependencies for diamond shows good qualitative agreement.

Optical and EPR spectroscopy of Er3+ in lithium yttrium borate, Li6Y(BO3)3:Er single crystals

The energy levels of Er3+ ions have been determined in lithium yttrium borate (Li6Y(BO3)3) single crystals in a wide spectral range between 6000 and 40000 cm−1 together with an analysis of the ground state, using optical and EPR spectroscopy. The crystal field splittings of the 4I15/2 ground state and those of nearly all excited states up to the 4D7/2 manifold have been obtained at low temperature from luminescence (T = 5 K) and absorption (T = 9 K) measurements, respectively. The numbers of experimentally observed Stark sublevels agree well with those expected theoretically for Er3+ ions occupying a single low symmetry (C1) site. A full set of g- and 167Er hyperfine tensor parameters are presented for the ground state characterized by EPR; the measured Orbach-type spin-relaxation rates viz. the involved activation energies correspond to the optically derived lowest excited sublevels.