Electric Hyperfine Interactions Research Articles

First-principle study of the ground-state crystal structure and optoelectronic response of CsPbX3 (X= Cl, Br, I) for photovoltaic applications

The optoelectronic response and ground state crystal structure of tetragonal (P4/mbm), orthorhombic (Pmnb) and monoclinic (P21/m) phases of CsPbX3 (X = Cl, Br, I) are studied for optoelectronic applications using first principle simulations. Electric field gradient (EFG) and magnetic hyperfine interactions are investigated to explore the charge distributions surrounding the nucleus and local magnetic environment of the atomic nucleus. The orthorhombic phase of these compounds is more stable having lowest ground-state energy compared to tetragonal and monoclinic phases. The understudied halide perovskites have direct band gap nature and spin orbit coupling (SOC) effect splits Pb-p and X-p orbitals at the edges of conduction and valence band (CB and VB) respectively. At the edge of VB, the strongly hybridized X-p and Pb-p orbital and direct band gap nature of CsPbX3 is excellent for the light absorption and photovoltaic (PV) applications. The n-i-p configuration (FTO/ETL/CsPbX3/HTL/Au) of the simulated structure shows that CsPbI3 has improved power conversion efficiency (PCE) of 22.48 % and 22.32 % and quantum efficiency (QE) about ∼80 % in tetragonal and monoclinic phases respectively. The Pb and Cs values of EFG tensor in z-direction (Vzz) are close to each other, which show that the distribution of electronic charge density is similar near these nuclei. Moreover, Cs-s orbital has negligible contribution and Pb-p and I-p orbitals have higher contribution in the hyperfine field (HFF). The negative HFF indicates the opposite HFF contribution.

The Parameters of the Hyperfine Structure of 57Fe Nuclei in FeBO3 and Fe0.91Ga0.09BO3 Single Crystals

The parameters of the hyperfine interaction of 57Fe nuclei in single crystals of iron borate FeBO3 and its isostructural solid solution Fe0.91Ga0.09BO3 have been determined by Mössbauer spectroscopy. A theoretical model has been developed to describe resonant transitions of iron nuclei in the approximation of a combined magnetic dipole and electric quadrupole hyperfine interaction, taking into account the statistical distribution of Ga and Fe over octahedral positions in the Fe0.91Ga0.09BO3 crystal. It has been established that even a low Ga concentration leads to a significant change in the hyperfine structure of the 57Fe nuclei inFeBO3, which manifests itself in the appearance of additional components in the Mössbauer spectra of the Fe0.91Ga0.09BO3 single crystal.

Ab initio calculations of the hyperfine structure of 109Cd, 109Cd+ and reevaluation of the nuclear quadrupole moment Q(109Cd)

Large scale ab initio calculations of the electric contribution (i.e. the electric field gradient (EFG)) to the electric quadrupole hyperfine interaction constants B for the state of 109Cd+ ion and the states of neutral 109Cd atom were performed. To probe the sensitivity of B to different electron correlation effects, six sets of variational multi-configuration Dirac–Hartree–Fock and relativistic configuration interaction calculations employing different strategies were carried out. The calculated EFGs, together with experimental values of B, allow us to extract a new value of the nuclear electric quadrupole moment Q(109Cd) = 0.634(22) b which is about 5% larger than the recommended value (Stone 2016 At. Data Nucl. Data Tables 111–112 1; Pyykkö 2018 Mol. Phys. 116 1328). Efforts were made to provide a realistic theoretical uncertainty for the final Q value based on statistical principles and correlation with the magnetic dipole hyperfine interaction constant A.

Magnetic and electric hyperfine parameters of antiferromagnet FеBO3 intended for monochromatization of synchrotron radiation

In this work, Mössbauer spectroscopy and X-ray diffraction were used to determine the precision values of the hyperfine interaction parameters and the crystal structure of FeBO3 single crystals in a wide temperature range, including the region of magnetic phase transitions (TN). A theoretical model has been developed to describe nuclear resonance transitions in iron atoms in the approximation of a combined magnetic dipole and electric quadrupole hyperfine interaction. A technique for correcting the Mössbauer spectra, considering the effective thickness of the absorber, has also been elaborated.It is shown that the appearance of two additional resonance lines in the hyperfine structure significantly affects the shape of the FeBO3 spectra near the N é el temperature (ТN). The characteristic Debye temperatures for Fe and B cations in the iron borate structure have been determined. The developed technique and the results obtained are extremely important for the use of FeBO3 crystals in new high-tech branches of science and technology, including optoelectronics and synchrotron technologies.

Imaging and sensing of pH and chemical state with nuclear-spin-correlated cascade gamma rays via radioactive tracer

Single-photon-emission computed tomography (SPECT) and positron-emission tomography (PET) are highly sensitive molecular detection and imaging techniques that generally measure accumulation of radio-labeled molecules by detecting gamma rays. Quantum sensing of local molecular environment via spin, such as nitrogen vacancy (NV) centers, has also been reported. Here, we describe quantum sensing and imaging using nuclear-spin time-space correlated cascade gamma-rays via a radioactive tracer. Indium-111 (111In) is widely used in SPECT to detect accumulation using a single gamma-ray photon. The time-space distribution of two successive cascade gamma-rays emitted from an 111In atom carries significant information on the chemical and physical state surrounding molecules with double photon coincidence detection. We propose and demonstrate quantum sensing capability of local micro-environment (pH and chelating molecule) in solution along with radioactive tracer accumulation imaging, by using multiple gamma-rays time-and-energy detection. Local molecular environment is extracted through electric quadrupole hyperfine interaction in the intermediate nuclear spin state by the explicit distribution of sub-MeV gamma rays. This work demonstrates a proof of concept, and further work is necessary to increase the sensitivity of the technique for in vivo imaging and to study the effect of scattered radiation for possible application in nuclear medicine.

Measurements of the Hyperfine Structure of Atomic Energy Levels in Co ii

Abstract Analysis of hyperfine structure constants of singly ionized cobalt (Co II) were performed on cobalt spectra measured by Fourier transform spectrometers in the region 3000–63,000 cm−1 (33333 – 1587 Å). Fits to over 700 spectral lines led to measurements of 292 magnetic dipole hyperfine interaction A constants, with values between −32.5 mK and 59.5 mK (1 mK = 0.001 cm−1). Uncertainties of 255 A constants were between ±0.4 mK and ±3.0 mK, the remaining 37 ranged up to ±7 mK. The electric quadrupole hyperfine interaction B constant could be estimated for only one energy level. The number of Co II levels with known A values has now increased tenfold, improving and enabling the wider, more reliable, and accurate application of Co II in astronomical chemical abundance analyses.

Structure of the 11/2− isomeric state in La133

We report measurement of the $g$-factor for the ${11/2}^{\ensuremath{-}}$ isomeric state at 535 keV in $^{133}\mathrm{La}$, employing the time differential perturbed angular distribution technique (TDPAD). This isomer was populated in the reaction $^{126}\mathrm{Te}(^{11}\mathrm{B}$, $4n)^{133}\mathrm{La}$ at beam energy of 52 MeV. From the observed nuclear spin precession, analysed through combined, magnetic dipole and electric quadrupole hyperfine interactions, we obtain the $g$ factor for the $11/{2}^{\ensuremath{-}}$ state as $g=1.16\ifmmode\pm\else\textpm\fi{}0.07$. In addition, this analysis provides the spectroscopic quadrupole moment $|Q|=1.71\ifmmode\pm\else\textpm\fi{}0.34\phantom{\rule{3.33333pt}{0ex}}b$, yielding the deformation parameter $\ensuremath{\beta}=0.28\ifmmode\pm\else\textpm\fi{}0.10$. Further, we have performed theoretical calculations using the large-scale shell model and the Monte Carlo shell model. The results successfully describe the low-lying levels and the band structures of $^{133}\mathrm{La}$, and the calculated $g$ factor compares well with the values obtained from our experiment. The dominant configuration of $11/{2}^{\ensuremath{-}}$ isomeric state in $^{133}\mathrm{La}$ is inferred to be $\ensuremath{\pi}({h}_{11/2})\ensuremath{\bigotimes}^{132}\mathrm{Ba}({0}^{+})$.

Determination of the electric field gradient and the magnetic field in M\xf6ssbauer spectroscopy

Problem of unambiguous determination of all components of the electric field gradient and hyperfine magnetic field in case of mixed hyperfine interaction was solved for the first time. Concept of a new method to determine orientation of hyperfine fields in the absorber Cartesian frame for Mössbauer spectroscopy for nuclear transitions between levels with spin 3/2 and 1/2 is presented. The method can be applied for single-crystal absorbers with well separated absorption lines in their spectra. Explicit formulas derived from velocity moments are presented. The new method allows full separation of the electric quadrupolar and magnetic dipolar hyperfine interactions by using unpolarized radiation.

Probe Mössbauer Spectroscopy of BiNi0.9657Fe0.04O3

This paper presents results of a 57Fe probe Mossbauer spectroscopy study of the BiNi0.9657Fe0.04O3 nickelate. The spectra measured above its TN demonstrate that Fe3+ cations heterovalently substitute for Ni2+ nickel (←Fe3+), being stabilized on four sites of the nickel sublattice in the structure of BiNiO3. Calculations in an ionic model with allowance for monopole and dipole contributions to the electric field gradient indicate that the parameters of electric hyperfine interactions between 57Fe probe atom nuclei reflect the specifics of the local environment of the nickel in the structure of the unsubstituted BiNiO3 nickelate. Below TN, Mossbauer spectra transform into a complex Zeeman structure, which is analyzed in terms of first-order perturbation theory with allowance for electric quadrupole interactions as a small perturbation of the Zeeman levels of the 57Fe hyperfine structure, as well as for specific features of the magnetic ordering of the Ni2+ cations in the nickelate studied.

Experimental TDPAC and Theoretical DFT Study of Structural, Electronic, and Hyperfine Properties in (111In → )111Cd-Doped SnO2 Semiconductor: Ab Initio Modeling of the Electron-Capture-Decay After-Effects Phenomenon

In this paper we investigate the effect of Cd doping at ultralow concentrations in SnO2 both experimentally, by measuring the temperature dependence of the electric quadrupole hyperfine interactions with time-differential γ–γ perturbed angular correlation (TDPAC) spectroscopy using 111Cd as probe nuclei, and theoretically, by performing first-principles calculations based on the density functional theory. TDPAC spectra were successfully analyzed with a time-dependent on–off model for the perturbation factor. These results show combined dynamic plus static interactions whose electric-field-gradients were associated in this model to different stable electronic configurations close to the Cd atoms. The dynamic regime is then originated in fast fluctuations between these different electronic configurations. First-principles calculation results show that the Cd impurity introduces a double acceptor level in the top of the valence band of the doped semiconductor and produces isotropic outward relaxations of the nearest oxygen neighbors. The variation of the calculated electric-field gradient tensor as a function of the charge state of the Cd impurity level shows an interesting behavior that explains the experimental results, giving strong support from first-principles to the electron-capture after-effects proposed scenario. The electron-capture decay of the parent 111In to 111Cd as well as the double acceptor character of the 111Cd impurity and the electric nature of the host are shown to contribute to the existence of these types of time-dependent hyperfine interactions.

Dynamic quadrupole interactions in semiconductors

The time differential perturbed angular correlation, TDPAC, technique has been used for several decades to study electric quadrupole hyperfine interactions in semiconductors such as dynamic quadrupole interactions (DQI) resulting from after-effects of the nuclear decay as well as static quadrupole interactions originating from static defects around the probe nuclei such as interstitial ions, stresses in the crystalline structure, and impurities. Nowadays, the quality of the available semiconductor materials is much better, allowing us to study purely dynamic interactions. We present TDPAC measurements on pure Si, Ge, GaAs, and InP as a function of temperature between 12 K and 110 K. The probe 111In (111Cd) was used. Implantation damage was recovered by thermal annealing. Si experienced the strongest DQI with lifetime, τg, increasing with rising temperature, followed by Ge. In contrast, InP and GaAs, which have larger band gaps and less electron concentration than Si and Ge in the same temperature range, presented no DQI. The results obtained also allow us to conclude that indirect band gap semiconductors showed the dynamic interaction, whereas the direct band gap semiconductors, restricted to GaAs and InP, did not.

Modulated magnetic structure of Fe3PO7 as seen by Fe57 Mössbauer spectroscopy

The paper reports new results of the 57Fe M\"ossbauer measurements on Fe3PO4O3 powder sample recorded at various temperatures including the point of magnetic phase transition TN ~ 163K. The spectra measured above TN consist of quadrupole doublet with high quadrupole splitting of D300K ~ 1.10 mm/s, emphasizing that Fe3+ ions are located in crystal positions with a strong electric field gradient (EFG). In order to predict the sign and orientation of the main components of the EFG tensor we calculated monopole lattice contributions to the EFG. In the temperature range T < TN, the experimental spectra were fitted assuming that the electric hyperfine interactions are modulated when the Fe3+ spin (S) rotates with respect to the EFG axis and emergence of spatial anisotropy of the hyperfine field Hhf = S\~AI at 57Fe nuclei. These data were analyzed to estimate the components of the anisotropic hyperfine coupling tensor (\~A). The large anharmonicity parameter, m ~ 0.94, of the spiral spin structure results from easy-axis anisotropy in the plane of the iron spin rotation. The temperature evolution of the hyperfine field Hhf(T) was described by Bean-Rodbell model that takes into account that the exchange magnetic interactions are strong function of the lattice spacing. The obtained M\"ossbauer data are in qualitative agreement with previous neutron diffraction data for a modulated helical magnetic structure in strongly frustrated Fe3PO4O3.

Theoretical study of the hyperfine-interaction constants and the isotope-shift factors for the 3s21S0–3s3p3,1P1o transitions in Al+

We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3s3p $^{3,1}P^o_1$ states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3s$^2~^1S_0$ in Al$^+$ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the CC and the higher-order correlations are considerable for evaluating the uncertainties of the atomic parameters concerned. The uncertainties of the hyperfine interaction constants in this work are less than 1.5\%. Although the isotope shift factors are highly sensitive to the electron correlations, reasonable uncertainties were obtained by exploring the effects of the electron correlations. Moreover, we found that the relativistic nuclear recoil corrections to the mass shift factors are very small and insensitive to the electron correlations for Al$^{+}$. These atomic parameters present in this work are valuable for extracting the nuclear electric quadrupole moments and the mean-square charge radii of Al isotopes.

A study of magnetic and electronic hyperfine interactions in epitaxial film of yttrium-iron garnet by the method of conversion electron Mössbauer spectroscopy

Magnetic and electric hyperfine interactions in the near-surface layers of epitaxial films of yttrium-iron garnet of the (111) orientation grown by the liquid-phase epitaxy method are studied by the method of the conversion electron Mossbauer spectroscopy (CEMS). The studies reveal a stoichiometric violation of the anion sublattice in the near-surface layers (≈8 × 10–8 m) of yttrium iron garnet film and, as a consequence, the formation of two types of d-sites, which is associated with a significant concentration of point defects in the anion sublattice of the near-surface area and the growing weight of the covalent bonding in the transition film–air layer. This also causes the presence of a fixed doublet component corresponding to iron ions in a paramagnetic state with an intermediate degree of valency between +2 and +3. It is shown that interpretation of the spectroscopic results using the Hamiltonian of mixed magnetic and quadrupole interactions makes it possible to obtain a vector diagram of the spatial orientations of the effective magnetic fields at the Fe57 nuclei and, as a consequence, to reconstruct the formation mechanism of the resulting vector of the magnetic moment of the yttrium iron garnet epitaxial film. Our studies reveal a slight noncollinearity of ≈4° in the orientations of the magnetic moments in the a- and d-sites of iron. The obtained results complement the picture of the magnetic and electronic hyperfine interactions in the epitaxial ferrite-garnet films and should be considered in the practical applications of the magnetic properties of such materials.

Experimental Investigation of the Hyperfine Structure of Neutral Praseodymium Spectral Lines and Discovery of New Energy Levels

Experimental investigations of Pr I spectral lines were performed by means of laser induced fluorescence spectroscopy, using a hollow cathode discharge lamp as source of free atoms. The wavelengths for the laser excitation were found by the help of a highly resolved Fourier transform spectrum. Altogether we excited 236 unclassified lines and analysed their hyperfine structure, which led, together with the measured wavelengths of the observed fluorescence lines, to the discovery of 32 new even parity and 38 odd parity fine structure energy levels. These levels allow to classify more than 670 spectral lines of Pr I. The wave number calibrated Fourier transform spectrum allowed us to determine the energies of most of these newly discovered levels with an uncertainty of 0.015 cm-1. Angular momenta, parity, and magnetic and electric hyperfine interaction constants (A and B) of the new levels were also determined.

The Nitrogenase FeMo-Cofactor Precursor Formed by NifB Protein: A Diamagnetic Cluster Containing Eight Iron Atoms.

The biological activation of N2 occurs at the FeMo-cofactor, a 7Fe-9S-Mo-C-homocitrate cluster. FeMo-cofactor formation involves assembly of a Fe6-8 -SX -C core precursor, NifB-co, which occurs on the NifB protein. Characterization of NifB-co in NifB is complicated by the dynamic nature of the assembly process and the presence of a permanent [4Fe-4S] cluster associated with the radical SAM chemistry for generating the central carbide. We have used the physiological carrier protein, NifX, which has been proposed to bind NifB-co and deliver it to the NifEN protein, upon which FeMo-cofactor assembly is ultimately completed. Preparation of NifX in a fully NifB-co-loaded form provided an opportunity for Mössbauer analysis of NifB-co. The results indicate that NifB-co is a diamagnetic (S=0) 8-Fe cluster, containing two spectroscopically distinct Fe sites that appear in a 3:1 ratio. DFT analysis of the (57) Fe electric hyperfine interactions deduced from the Mössbauer analysis suggests that NifB-co is either a 4Fe(2+) -4Fe(3+) or 6Fe(2+) -2Fe(3+) cluster having valence-delocalized states.

The Nitrogenase FeMo‐Cofactor Precursor Formed by NifB Protein: A Diamagnetic Cluster Containing Eight Iron Atoms

AbstractThe biological activation of N2 occurs at the FeMo‐cofactor, a 7Fe–9S–Mo–C–homocitrate cluster. FeMo‐cofactor formation involves assembly of a Fe6–8–SX–C core precursor, NifB‐co, which occurs on the NifB protein. Characterization of NifB‐co in NifB is complicated by the dynamic nature of the assembly process and the presence of a permanent [4Fe–4S] cluster associated with the radical SAM chemistry for generating the central carbide. We have used the physiological carrier protein, NifX, which has been proposed to bind NifB‐co and deliver it to the NifEN protein, upon which FeMo‐cofactor assembly is ultimately completed. Preparation of NifX in a fully NifB‐co‐loaded form provided an opportunity for Mössbauer analysis of NifB‐co. The results indicate that NifB‐co is a diamagnetic (S=0) 8‐Fe cluster, containing two spectroscopically distinct Fe sites that appear in a 3:1 ratio. DFT analysis of the 57Fe electric hyperfine interactions deduced from the Mössbauer analysis suggests that NifB‐co is either a 4Fe2+–4Fe3+ or 6Fe2+–2Fe3+ cluster having valence‐delocalized states.

High-resolution magneto-optical spectroscopy ofLiYF47:Er3+167,Er3+166and analysis of hyperfine structure of ultranarrow optical transitions

We performed high-resolution magneto-optical spectroscopy of the hyperfine transitions from $^{4}I_{15/2}$ to the $^{4}I_{13/2}$ and $^{4}I_{9/2}$ multiplets of $^{167}\mathrm{Er}^{3+}$ and $^{166}\mathrm{Er}^{3+}$ in an isotopically purified $^{7}\mathrm{LiYF}_{4}$ crystal in various external magnetic fields up to 0.7 T. The obtained experimental results are interpreted in the framework of the generalized theoretical approach. The derived model successfully explains all the experimentally observed optical hyperfine transitions by using a single set of basic parameters found for the crystal-field interaction, magnetic dipole and electric quadrupole hyperfine interactions, together with Zeeman interactions at different orientations of the external magnetic field. A number of the studied quantum transitions appears to be promising for use in Raman quantum storage at optical telecommunication wavelengths.

Hyperfine interactions of 57Fe impurity nuclei in multiferroic CuCrO2

Hyperfine interactions of 57Fe nuclei in multiferroic CuCrO2 are studied by means of Mossbauer probe spectroscopy in a wide range of temperatures, including that of the magnetic phase transition. The temperature dependences of the parameters of electric and magnetic hyperfine interactions and the anharmonicity parameter of the spin wave are obtained as part of the spatial anharmonic spin-modulated structure.

Local electronic and magnetic properties of pure and Mn-containing magnetocaloric LaFe13−xSix compounds inferred from Mössbauer spectroscopy and magnetometry

Manganese containing La–Fe–Si alloys are important magnetocaloric compounds, since Mn atoms prevent segregation of hydrogen in partially hydrogenated La–Fe–Mn–Si alloys when their Curie temperature is tuned to room temperature by hydrogen. The effect of Mn alloying on the Fe atomic magnetic moment μFe is still rather unexplored. Therefore, we investigated the (local) magnetic and electric hyperfine interactions in the strongly magnetocaloric compound LaFe11.3Mn0.3Si1.4 and, for comparison, LaFe11.6Si1.4 by 57Fe Mössbauer spectroscopy, and the global magnetic properties by vibrating sample magnetometry. The NaZn13 structure was confirmed by x-ray diffraction. Two non-equivalent Fe lattice sites are known to exist in this material: the (96i) sites (FeII) of low local symmetry, and the highly symmetrical (8b) sites (FeI). At room temperature in the paramagnetic state, the electric hyperfine parameters of Fe atoms on both sites were obtained. At low temperatures (4.8 K), the observed magnetically split nuclear Zeeman sextets with broad apparent lines were analyzed in terms of a distribution P(Bhf) of hyperfine magnetic fields Bhf. The average hyperfine field 〈Bhf〉, originating predominantly from FeII sites, was found to be rather high (30.7(1) T at 4.8 K) for LaFe11.6Si1.4, and the approximate relation 〈Bhf〉 = AμFe is confirmed for FeII sites, with A = 14.2 T/μB. 〈Bhf〉 is significantly reduced (to 27.7(1) T at 4.8 K) for the Mn-containing sample LaFe11.3Mn0.3Si1.4, providing evidence for a reduction by 9.7% of the average Fe atomic moment μFe from ~2.16 μB to a value of ~1.95 μB by Mn substitution of Fe. Our Mössbauer results are in good agreement with magnetometry, which reveals a reduction of the saturation magnetization of Ms = 163.1(1) Am2 kg−1 of LaFe11.6Si1.4 by 10.5% due to Mn substitution.