Oxidation and magnetic states of chalcopyrite CuFeS2: a first principles calculation

The ground state band structure, magnetic moments, charges and population numbers of electronic shells of Cu and Fe atoms have been calculated for chalcopyrite CuFeS2 using density functional theory. The comparison between our calculation results and experimental data (X ray photoemission, X ray absorption and neutron diffraction spectroscopy) has been made. Our calculations predict a formal oxidation state for chalcopyrite as Cu1+Fe3+S. However, the assignment of formal valence state to transition metal atoms appears to be oversimplified. It is anticipated that the valence state can be confirmed experimentally by nuclear magnetic and nuclear quadrupole resonance and Mössbauer spectroscopy methods

Mössbauer forward scattering: time-domain spectra

© 2016, Springer International Publishing Switzerland.The transmission of the Mössbauer radiation through an absorber being in the acoustic oscillation mode under forward scattering (FS) conditions has been analyzed. The modification of the existing models of the FS spectra (frequency and time) formation to the case of the arbitrary phase correlation of nuclear oscillations in the sample has been proposed. An adequate description of the time delayed experiments with the 57Fe Mössbauer resonance using the modulation of the single-photon wave packet by acoustic field has been obtained. One has been done in the frame of the Raman scattering of Mössbauer photons. The models extended this way can be used to control the degree of phase correlation of nuclear oscillations (or other processes) induced in the sample by external fields

A novel data on Ag5SbS4 and CuPbSbS3 probed by antimony NQR spectroscopy

Investigations of Sb-based chalcogenides, stephanite Ag5SbS 4 and bournonite CuPbSbS 3, have been performed by 121,123Sb nuclear quadrupole resonance (NQR). In stephanite a phase transition at 140 K and internal diffusion motions with an activation energy of 0.29 eV have been experimentally detected. The analysis of experimental results for bournonite revealed two crystal-chemical positions of Sb in the unit cell with distinct local symmetry. The NQR frequencies ν and line-widths Δν data indicate that Sb(A)S3 complex has almost axial symmetry, but Sb(B)S 3 complex is substantially distorted

Electronic structure and indirect spin-spin interactions in bournonite (CuPbSbS3) according to antimony nuclear quadrupole resonance

A complex sulfide CuPbSbS3 (bournonite) has been studied by the nuclear quadrupole resonance on 121,123Sb. The temperature dependences of the spectroscopic and relaxation parameters in the temperature range of 10-295 K have been obtained. The crystallochemical features of the environment of the two non-equivalent Sb positions in the unit cell have been revealed from the nuclear quadrupole resonance spectra. The existence of the lattice vibrations with the frequency ω = 110 cm-1 has been demonstrated on the basis of the temperature dependence of the nuclear quadrupole resonance frequencies. Slow beats have been observed on the decay curve of the spin echo signal. Experimental data have been analyzed in order to reveal the existence of the indirect spin-spin interactions involving Sb atoms. The indirect spin-spin coupling constant has been estimated as J = 2.5 ± 0.5 kHz. © 2013 Pleiades Publishing, Ltd

Structure and transport properties of stephanite (Ag 5SbS 4) according to antimony nuclear quadrupole resonance

Silver sulfo-antimonide Ag 5SbS 4 (stephanite) has been studied by nuclear quadrupole resonance (NQR) spectroscopy on antimony nuclei. The temperature dependences of the spectroscopic and relaxation parameters have been examined in the range of 4. 2-395 K. A phase transition at 140 K and internal motions with an activation energy of 0. 29 eV have been experimentally detected. The nature of the phase transition and diffusion of silver ions has been discussed in view of the reported data. © 2012 Pleiades Publishing, Ltd

Polarization analysis for the thermal chopper spectrometer TOPAS

© 2015 Owned by the authors, published by EDP Sciences. We report on the progress of the construction of the thermal time-of-flight spectrometer with polarization analysis TOPAS at the Mayer-Leibnitz Zentrum (MLZ). The instrument components approach the status to be ready for installation. The special feature of the instrument is its capability for wide-angle polarization analysis in the thermal spectral range. Here we describe a novel approach to rotate the neutron spin adiabatically into the X, Y or Z direction of the laboratory frame by combination of permanent magnets aligned as Halbach rings and electrically generated fields. Despite the severe spatial restrictions the design exhibits a very high adiabaticity and interacts only weakly with the coil layout for the analyzing 3He spin filter cell (SFC)

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

Nuclear resonance methods, including Mössbauer spectroscopy, are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed

Oxidation and magnetic states of chalcopyrite CuFeS2: A first principles calculation

The ground state band structure, magnetic moments, charges and population numbers of electronic shells of Cu and Fe atoms have been calculated for chalcopyrite CuFeS2 using density functional theory. The comparison between our calculation results and experimental data (X-ray photoemission, X-ray absorption and neutron diffraction spectroscopy) has been made. Our calculations predict a formal oxidation state for chalcopyrite as Cu 1+Fe3+S2 2-. However, the assignment of formal valence state to transition metal atoms appears to be oversimplified. It is anticipated that the valence state can be confirmed experimentally by nuclear magnetic and nuclear quadrupole resonance and Mössbauer spectroscopy methods. © 2014 Pleiades Publishing, Ltd

Copper valence, structural separation and lattice dynamics in tennantite (fahlore): NMR, NQR and SQUID studies

Electronic and magnetic properties of tennantite subfamily of tetrahedrite-group minerals have been studied by copper nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR) and SQUID magnetometry methods. The temperature dependences of copper NQR frequencies and line-width, nuclear spin-lattice relaxation rate T1 -1 and nuclear spin-echo decay rate T2 -1 in tennantite samples in the temperature range 4.2-210 K is evidence of the presence of field fluctuations caused by electronic spins hopping between copper CuS3 positions via S2 bridging atom. The analysis of copper NQR data at low temperatures points to the magnetic phase transition near 65 K. The magnetic susceptibility in the range 2-300 K shows a Curie-Weiss behavior, which is mainly determined by Fe2+ paramagnetic substituting ions. © Springer-Verlag 2007

Contribution of copper Nqr spectroscopy to the geological studies of complex sulfides and oxides

Many energy-related areas such as nuclear waste isolation, continental drilling, fossil fuel recovery, and geothermal energy are directly associated with an in-depth understanding of the earth sciences. Of particular interest is the development of analytical techniques which can augment existing ones in developing a better understanding of mineralogy. Presently, available instrumental techniques for studying mineralogical problems such as x-ray, electron and neutron diffraction, nuclear gamma resonance (NGR or Mössbauer spectroscopy), electron microscopy and transmission electron microscopy have inherent limitations. These manifest themselves in being unable to characterize mineral samples fully, especially if they are polycrystalline. Nuclear Quadrupole Resonance (NQR) spectroscopy offers the potential for being able to obtain accurate high resolution spectra. These can then be interpreted to give structural information which can be related to local electronic structure, atomic arrangement, order/disorder phenomena, and crystal phase transformation. In addition, internal dynamics (ionic diffusion, metallic behavior, rotations, and so on) in the solid state can be studied. Furthermore, since NQR data are sensitive to changes in temperature and pressure, there is the possibility of obtaining stress/strain information. As applied to mineralogical and geological problems, NQR can also provide additional information, for example: chemical activity of minerals (genetic and technological aspects) at different hydrothermal conditions, the studies of impurity configurations in ore minerals and their distribution in crystal lattice, and other. This chapter highlights some NQR studies in copper sulfides, which demonstrate how NQR method can contribute to our understanding of geological problems. Examples are taken primarily from author's investigate groups. © 2009 Springer Science+Business Media B.V