Low Spin Research Articles

Dehydration Achieving the Iron Spin State Regulation of Prussian Blue for Boosted Sodium-Ion Storage Performance.

Prussian blue analogs (PBAs) show promise as cathodes for sodium-ion batteries due to their notable cycle stability, cost-effectiveness, and eco-friendly nature, yet the presence of interstitial water limits the specific capacity and obstructs Na+ mobility within the material. Although considerable experimental efforts are focused on dehydrating water for capacity enhancement, there is still a deficiency of a comprehensive understanding of the low capacity of low-spin Fe resulting from interstitial water, which holds significance in Na+ storage. This study introduces a novel gas-assisted heat treatment method to efficiently remove interstitial water from Fe-based PBA (NaFeHCF) electrodes and combines experiments and theoretical calculations to reveal the iron spin state regulation that is related to the capacity enhancement mechanism. This dehydration strategy significantly enhances battery capacity, especially the portion at higher voltages (3.4-4.0V). The increase in capacity is attributed to the following factors: an enhanced proportion of Fe2+, reduced water content which facilitates faster charge transfer, and the activation of low spin Fe2+. The optimized NaFeHCF demonstrated impressive half-cell performance of retaining 87.3% capacity after 2000 cycles at a 5C rate and achieving 100mAhg-1 capacity over 200 cycles when being paired with hard carbon, exhibiting its practical potential.

Spin-selective transport in a correlated double quantum dot-Majorana wire system

In this work we investigate the spin-dependent transport through a double quantum dot embedded in a ferromagnetic tunnel junction and side attached to a topological superconducting nanowire hosting Majorana zero-energy modes. We focus on the transport regime when the Majorana mode leaks into the double quantum dot competing with the two-stage Kondo effect and the ferromagnetic-contact-induced exchange field. In particular, we determine the system’s spectral properties and analyze the temperature dependence of the spin-resolved linear conductance by means of the numerical renormalization group method. Our study reveals unique signatures of the interplay between the spin-resolved tunneling, the Kondo effect and the Majorana modes, which are visible in the transport characteristics. In particular, we uncover a competing character of the coupling to topological superconductor and that to ferromagnetic leads, which can be observed already for very low spin polarization of the electrodes. This is signaled by an almost complete quenching of the conductance in one of the spin channels which is revealed through perfect conductance spin polarization. Moreover, we show that the conductance spin polarization can change sign depending on the magnitude of spin imbalance in the leads and strength of interaction with topological wire. Thus, our work demonstrates that even minuscule spin polarization of tunneling processes can have large impact on the transport properties of the system.

Spin dynamics investigation and structural analysis of ambient scalable Sr2+ doped zirconium ferrite nanoparticles synthesized by low temperature auto combustion route

Microwave spin resonance behaviour of Sr2+ doped Zirconium ferrite Zr1-xSrxFe2O4; (0 ≤ x ≥ 0.20) nanoparticles synthesized by auto combustion route has been investigated by electron paramagnetic resonance (EPR) which show a broad ferromagnetic resonance signal with a superimposed hump signal which is attributed to ferrite Fe3+ ions and oxygen vacancies which is in agreement with XRD and XPS. EPR shows low spin concentration and smaller relaxation time for Zr0.80Sr0.20Fe2O4 which can be used for hyperthermia and for use as a MRI contrast agent. EDS and XPS confirms the presence of Zr, Sr, Fe, O, and C and HRTEM images confirm growth along (220) and (311) with an interatomic distance of 0.3327 nm and 0.2622 nm respectively, thus, authenticating the formation of spinel structure in agreement with FTIR studies. The magnetic behaviour (M − H loop) shows high saturation magnetization and higher value of effective magnetocrystalline anisotropy (Keff) for Zr0.80Sr0.20Fe2O4.

Watching a Single Enzyme at Work Using Single-Molecule Surface-Enhanced Raman Scattering and DNA Origami-Based Plasmonic Antennas.

The detection of a single-enzyme catalytic reaction by surfaced-enhanced Raman scattering (SERS) is presented by utilizing DNA origami-based plasmonic antennas. A single horseradish peroxidase (HRP) was accommodated on a DNA origami nanofork plasmonic antenna (DONA) containing gold nanoparticles, enabling the tracing of single-molecule SERS signals during the peroxide reduction reaction. This allows monitoring of the structure of a single enzymatic catalytic center and products under suitable liquid conditions. Herein, we demonstrate the chemical changes of HRP and the appearance of tetramethylbenzidine (TMB), which works as a hydrogen donor before and after the catalytic reaction. The results show that the iron in HRP adopts Fe4+ and low spin states with the introduction of H2O2, indicating compound-I formation. Density functional theory (DFT) calculations were performed for later catalytic steps to rationalize the experimental Raman/SERS spectra. The presented data provide several possibilities for tracking single biomolecules in situ during a chemical reaction and further developing plasmon-enhanced biocatalysis.

Missing local operators, zeros, and twist-4 trajectories

The number of local operators in a CFT below a given twist grows with spin. Consistency with analyticity in spin then requires that at low spin, infinitely many Regge trajectories must decouple from local correlation functions, implying infinitely many vanishing conditions for OPE coefficients. In this paper we explain the mechanism behind this infinity of zeros. Specifically, the mechanism is related to the two-point function rather than the three-point function, explaining the vanishing of OPE coefficients in every correlator from a single condition. We illustrate our result by studying twist-4 Regge trajectories in the Wilson-Fisher CFT at one loop.

Common origin for black holes in both high mass X-ray binaries and gravitational-wave sources

Black-hole (BH) high-mass X-ray binary (HMXB) systems are likely to be the progenitors of BH-BH mergers detected in gravitational waves by LIGO/Virgo/KAGRA (LVK). Yet merging BHs reach higher masses ($ than BHs in HMXBs ($ and typically exhibit lower spins BH 0.25$ with a larger values tail) than what is often claimed for BHs in HMXBs BH 0.9$). This could suggest that these two classes of systems belong to different populations, but here we show that this may not necessarily be the case. The difference in masses is easily explained as the known HMXB-BHs are in galaxies with relatively high metallicity, so their progenitor stars are subject to strong mass loss from winds, leading to relatively low-mass BH at core collapse. Conversely, LVK is also able to detect BHs from low-metallicity galaxies that are known to naturally produce more massive stellar-origin BHs. However, the difference in spin is more difficult to explain. Models with efficient angular momentum transport in stellar interiors produce slowly spinning progenitors for both LVK and HMXB BHs. Known HMXBs have orbital periods that are too long for efficient tidal spin-up and are also unlikely to have undergone significant accretion spin-up. Instead, we show that the derived value of the BH spin depends strongly on how the HMXB accretion disc emission is modelled. We argue that since Cyg X-1 is never observed to be in a soft spectral state, the appropriate spectral models must take into account the Comptonisation of the disc photosphere. We show that such models are consistent with low spin values, namely: $a_ BH This was recently confirmed by other teams for both Cyg X-1 and LMC X-1 and here we show this is also the case for M33 X-7. We conclude that all known HMXB BHs can exhibit a low spin in accordance with the results of stellar evolution models. Hence, the observations presented in this work are consistent with the scenario where LVK BHs and HMXB BHs belong to the same population.

Spin state driven weighted mobility and thermal conductivity properties of electron (Hf) doped strongly correlated Mott insulator LaCoO3 for thermoelectric applications

Here, we report the temperature-dependent electrical resistivity and thermopower of hole (Sr) and electron (Hf) doped LaCoO3 in the range of 303–753 K. With increasing temperature, the insulating behavior (303–503 K) with dominance of small polaron hopping to metallic transition (>503 K) is observed. The electron doped sample shows an insulating behavior (19.5 Ω cm) and positive thermopower (139 μV K−1) value due to the spin state blockade, i.e., electron hopping from high spin Co2+ to low spin Co3+ is strongly inhibited. The calculated weighted mobility (μW) of 0.01 to 0.96 cm2 V−1 s−1 validates the observed spin blockade mechanism in electron doped LaCoO3. The fluctuation of spin/orbital ordering and point defect scattering results in the low thermal conductivity of 0.5 W m−1 K−1 for Hf doped LaCoO3. The spin state blockade observed in the electrical resistivity and low lattice thermal conductivity reveals that spin state transition drives the thermoelectric response in Mott insulator LaCoO3.

Innovative Mn3−xO4−y@NCA design: Leveraging Mn/O vacancies and amorphous architecture for enhanced sodium-ion storage

Manganese-based oxide electrode materials suffer from severe Jahn-Teller (J-T) distortion, leading to severe cycle instability in sodium ion storage. However, it is difficult to adjust the electron at d orbitals exactly to a low spin state to eliminate orbital degeneracy and suppress J-T distortion fundamentally. This article constructed concentration-controllable Mn/O coupled vacancy and amorphous network in Mn3O4 and coated it with nitrogen-doped carbon aerogel (Mn3−xO4−y@NCA). The existence of Mn/O vacancies has been confirmed by scanning transmission electron microscopy (STEM) and positron annihilation lifetime spectroscopy (PALS). Atomic absorption spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS) determine the most optimal ratio of Mn/O vacancies for sodium ion storage is 1:2. Density functional theory (DFT) calculations prove that Mn/O coupled vacancies with the ratio of 1:2 could exactly induce a low spin states and a d4 electron configuration of Mn, suppressing the J-T distortion successfully. The abundant amorphous regions can shorten the transport distance of sodium ions, increase the electrochemically active sites and improve the pseudocapacitance response. From the synergetic effect of Mn/O coupled vacancies and amorphous regions, Mn3−xO4−y@NCA exhibits an energy density of 37.5 W h kg−1 and an ultra-high power density of 563 W kg−1 in an asymmetric supercapacitor. In sodium-ion batteries, it demonstrates high reversible capacity and exceptional cycling stability. This research presents a new method to improve the Na+ storage performance in manganese-based oxide, which is expected to be generalized to other structural distortion.

Intrinsic and extrinsic relaxation mechanisms for controlling spin current intensity in Fe 100−x Co x /Ta bilayers

Controlling the damping parameter in metallic ferromagnetic thin films is a key step for spintronic applications in which spin currents are generated by spin pumping. The coexistence of two states with low and high damping constant values would allow to obtain states of high and low spin current intensity, respectively. We have fabricated Fe 100−x Co x /Ta (with nominal x = 0, 15, 20, 25, 30 and 35) bilayers in which the Fe 100−x Co x layers grow epitaxially and the Ta layer is polycrystalline. We have found the coexistence of Gilbert damping and two magnon scattering mechanisms linked to a sign change in the magnetocrystalline anisotropy constant that allows the manipulation of low and high intensity states of the measured inverse spin Hall effect voltage. Bilayers with lower Co concentrations ( x⩽ 25%) present different relaxation mechanisms (isotropic Gilbert damping and two magnon scattering) and an extra ferromagnetic resonance linewidth broadening produced due to mosaicity. Bilayers with Co concentration x> 25% present a dominating Gilbert damping for all directions in the film plane. However, in this concentration range the damping constant is anisotropic and when the magnetic field is applied along the hard magnetization direction α increases ∼420% with respect to the value obtained for the easy magnetization direction. Coexistence of isotropic Gilbert damping and two magnon scattering generated spin currents 2.5 times larger when the field is applied along the hard magnetization axis compared to the value observed in the easy magnetization axis. Thesefindings make the Fe 100−x Co x /Ta system an excellent candidate for spintronic device applications.

Unraveling the nature of local field distortion-induced dual electron-trapping centers for efficient photocatalytic fuel evolution

Active electron-trapping centers play significant roles in photocatalysis. Herein, we synergize local field distortion and defects in nanocrystals to produce dual electron-trapping centers and unravel the nature of aluminum doping in porous ZnO with tunable amounts of heteroatoms and oxygen vacancies. The introduced Al atoms in the structural domain induce local field distortion and trigger the movement of Zn2+ from a singlet low spin state to a stable triplet state, resulting in the generation of free carriers trapping centers and optimized electronic energy band structure. Dual active electron-trapping centers of heteroatoms and oxygen vacancies promote the Separation of photo-generated charge carriers and reduce the adsorption energies of H* species. Furthermore, the d-band center of Al-doped ZnO with oxygen vacancies shifts to a higher energy position, thus promoting the adsorption and desorption of hydrogen intermediates and exhibiting 4-fold the photocatalytic H2 efficiency of pristine ZnO. This study provides new insights into the rational design of highly efficient oxide-based photocatalysts toward sustainable solar fuel evolution.

Low spin solutions of higher spin gravity: BPST instanton

Higher spin gravities do not have a low energy limit where higher-spin fields decouple from gravity. Nevertheless, it is possible to construct fine-tuned exact solutions that activate low-spin fields without sourcing the higher-spin fields. We show that BPST (Belavin-Polyakov-Schwartz-Tyupkin) instanton is an exact solution of Chiral Higher Spin Gravity, i.e. it is also a solution of the holographic dual of Chern-Simons matter theories. This gives an example of a low-spin solution. The instanton sources the opposite helicity spin-one field and a scalar field. We derive an Effective Field Theory that describes the coupling between an instanton and the other two fields, whose action starts with the Chalmers-Siegel action and has certain higher derivative couplings.

The 2018 Outburst of MAXI J1820+070 as Seen by Insight-HXMT

We present an analysis of the whole 2018 outburst of the black hole X-ray binary MAXI J1820+070 with Insight-HXMT data. We focus our study on the temporal evolution of the parameters of the source. We employ two different models to fit the disk’s thermal spectrum: the Newtonian model diskbb and the relativistic model nkbb. These two models provide different pictures of the source in the soft state. With diskbb, we find that the inner edge of the disk is close to the innermost stable circular orbit of a fast-rotating black hole and the corona changes geometry from the hard to the soft state. With nkbb, we find that the disk is truncated in the soft state and that the coronal geometry does not change significantly during the whole outburst. However, the model with nkbb can predict an untruncated disk around a fast-rotating black hole if we assume that the disk inclination angle is around 30° (instead of ∼60°, which is the inclination angle of the jet and is usually adopted as the disk inclination angle in the literature) and we employ a high-density reflection model. In such a case, we measure a high value of the black hole spin parameter with observations in the soft state, in agreement with the high spin value found from the analysis of the reflection features and in disagreement with the low spin value found by previous continuum-fitting method measurements with the disk inclination angle set to the value of the jet inclination angle.

Regulating Fe(III) spin state by anchoring iron on titanium dioxide for enhancing photo-Fenton treatment of tetracycline wastewater

Tetracycline (TC) wastewater can hardly be treated effectively by conventional processes due to its stable chemical structure and its refractoriness to biodegradation. Photo-Fenton technology based on iron-based catalyst exhibits excellent capacity on organic wastewater treatment, but current iron-based catalyst materials exist crucial problems such as slow regeneration of Fe(II) and low utilization of H2O2. In this study, Fe atom was anchored on TiO2 to regulate the spin state of Fe to prepare a new efficient photo-Fenton material. The results showed that the removal of TC by Fe2O3-TiO2(high spin, HS) can reach 94.7%, while the removal of TC by Fe-TiO2(low spin, LS) was only 83.0%. The Fe2O3-TiO2(HS) maintained high photo-Fenton activity after five cycles, and the TC removal rate still reached 91.8%. Fe2O3-TiO2(HS) had a narrow bandgap and excellent photogenerated charge separation properties, which facilitates the generation of photogenerated charges, improves the electron transfer, and accelerates the redox cycle of Fe(III)/Fe(II). The electrons in the 3d orbital of Fe2O3-TiO2(HS) are more easily to cross the antibonding orbital of the H2O2, which is conducive to the adsorption of H2O2 and generation of ·OH to accelerate TC degradation. This study provides a new photo-Fenton material for the treatment of TC wastewater and offers a new strategy for the development of photo-Fenton.

Lateral spin filter realized by monolayer Fe3GaTe2 and Fe3GaTe2/Graphene van der Waals heterostructures

Motivated by the lately discovered van der Waals ferromagnet Fe3GaTe2, a two-dimensional material with magnetic order and large perpendicular magnetic anisotropy above room temperature, we investigate two kinds of spin filters based on it. One is a flat pure Fe3GaTe2 monolayer and the other is a sandwich structure where the left and right parts are connected by a side-contacting graphene nanoribbon; both structures can be set in magnetic parallel or antiparallel configuration by external fields. Our first-principle calculation shows that the flat structure has large magnetoresistance (∼640 %) but relatively low spin filter efficiency (<50 %) at equilibrium, while the side-contacting structure shows a great enhancement in spin filter efficiency along with a relatively small magnetoresistance. Spin filter efficiency refers to the degree of spin polarization of the current passing through the device. For both structures, parallel configuration turns out to render a better filter than antiparallel configuration at equilibrium while the difference can be suppressed by applying a finite bias voltage. For side-contacting structure, different hybridization in different spins leads to very large spin filter efficiency (∼95.2 %) at equilibrium in parallel configuration, which may have a great potential in the application of future spintronics.

Crystal structure, properties and pressure-induced insulator-metal transition in layered kagome chalcogenides

Layered materials with kagome lattice have attracted a lot of attention due to the presence of nontrivial topological bands and correlated electronic states with tunability. In this work, we investigate a unique van der Waals (vdW) material system, A 2 M 3 X 4 (A = K, Rb, Cs; M = Ni, Pd; X = S, Se), where transition metal kagome lattices, chalcogen honeycomb lattices and alkali metal triangular lattices coexist simultaneously. A notable feature of this material is that each Ni/Pd atom is positioned in the center of four chalcogen atoms, forming a local square-planar environment. This crystal field environment results in a low spin state S= 0 of Ni2+/Pd2+. A systematic study of the crystal growth, crystal structure, magnetic and transport properties of two representative compounds, Rb2Ni3S4 and Cs2Ni3Se4, has been carried out on powder and single crystal samples. Both compounds exhibit nonmagnetic p-type semiconducting behavior, closely related to the particular chemical environment of Ni2+ ions and the alkali metal intercalated vdW structure. Additionally, Cs2Ni3Se4 undergoes an insulator-metal transition (IMT) in transport measurements under pressure up to 87.1 GPa without any structural phase transition, while Rb2Ni3S4 shows the tendency to be metalized.

M(TEIM) complexes with M as Co and Fe: Analogues of classic M(TIM)

The syntheses and characterization of Fe and Co complexes supported by a new tetra-imine macrocycle, TEIM (2,3,9,10-tetraethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene), are reported. Templating with Co(OAc)2·4H2O yielded trans-[Co(TEIM)Cl2][PF6] (1a), which was converted to trans-[Co(TEIM)X2][PF6] (X = N3 (2a) and NO2 (3a)) through reactions with NaX (X = N3 or NO2). Templating with Fe generated trans-[Fe(TEIM)(NCCH3)2][PF6]2, which was oxidized to trans-[Fe(TEIM)Cl2][PF6] (1b). The reaction of 1b with NaN3 formed [Fe(TEIM)(N3)2][PF6] (2b) while the reaction with [Fe(TEIM)(NCCH3)2][PF6]2 and NaNO2 yielded trans-[Fe(TEIM)(NO2)2] (3b). Single crystal X-ray diffraction studies revealed a pseudo-octahedral geometry around the Co / Fe centers with the ethyl groups oriented above or below the plane of the TEIM ring. The absorption spectra of 1b displays weak charge transfer bands near the UV to visible region, while 2b and 3b displayed intense charge transfer bands within the visible region. Cyclic voltammograms of 1a revealed four 1 e− reductions while those of 2a and 3a display only three cathodically shifted reductions. Analogous studies of 1b and 2b revealed two 1 e- reductions while 3b displays only an oxidation event. EPR studies of ferric complexes 1b and 2b indicated a low spin d5 electronic figuration with S = ½ ground state.

High Capacity and Fast Kinetics Enabled by Metal-Doping in Prussian Blue Analogue Cathodes for Sodium-Ion Batteries.

Prussian blue analogues (PBAs) have gained tremendous attention as promising low-cost electrochemically-tunable electrode materials, which can accommodate large Na+ ions with attractive specific capacity and charge-discharge kinetics. However, poor cycling stability caused by lattice strain and volume change remains to be improved. Herein, metal-doping strategy has been demonstrated in FeNiHCF, Na1.40Fe0.90Ni0.10[Fe(CN)6]0.85 ⋅ 1.3H2O, delivering a capacity as high as 148 mAh g-1 at 10 mA g-1. At an exceptionally high rate of 25.6 A g-1, a reversible capacity of ~55 mAh g-1 still can be obtained with a very small capacity decay rate of 0.02 % per cycle for 1000 cycles, considered one of the best among all metal-doped PBAs. This exhibits the stabilizing effect of Ni doping which enhances structural stability and long-term cyclability. In situ synchrotron X-ray diffraction reveals an extremely small (~1 %) change in unit cell parameters. The Ni substitution is found to increase the electronic conductivity and redox activity, especially at the low-spin (LS) Fe center due to inductive effect. This larger capacity contribution from LS Fe2+C6/Fe3+C6 redox couple is responsible for stable high-rate capability of FeNiHCF. The insight gained in this work may pave the way for the design of other high-performance electrode materials for sustainable sodium-ion batteries.

Quantification of the Donor-Acceptor Character of Ligands by the Effective Fragment Orbitals.

Metal-ligand interactions are at the heart of transition metal complexes. The Dewar-Chat-Duncanson model is often invoked, whereby the metal-ligand bonding is decomposed into the simultaneous ligand→metal electron donation and the metal→ligand back-donation. The separate quantification of both effects is not a trivial task, neither from experimental nor computational exercises. In this work we present the effective fragment orbitals (EFOs) and their occupations as a general procedure beyond the Kohn-Sham density functional theory (KS-DFT) framework for the identification and quantification of donor-acceptor interactions, using solely the wavefunction of the complex. Using a common Fe(II) octahedral complex framework, we quantify the σ-donor, π-donor, and π-acceptor character for a large and chemically diverse set of ligands, by introducing the respective descriptors σd, πd, and πa. We also explore the effect of the metal size, coordination number, and spin state on the donor/acceptor features. The spin-state is shown to be the most critical effect, inducing a systematic decrease of the sigma donation and π-backdonation going from low spin to high spin. Finally, we illustrate the ability of the EFOs to rationalize the Tolman electronic parameter and the trans influence in planar square complexes in terms of these new descriptors.

A continuous-wave and pulsed X-band electron spin resonance spectrometer operating in ultra-high vacuum for the study of low dimensional spin ensembles.

We report the development of a continuous-wave and pulsed X-band electron spin resonance (ESR) spectrometer for the study of spins on ordered surfaces down to cryogenic temperatures. The spectrometer operates in ultra-high vacuum and utilizes a half-wavelength microstrip line resonator realized using epitaxially grown copper films on single crystal Al2O3 substrates. The one-dimensional microstrip line resonator exhibits a quality factor of more than 200 at room temperature, close to the upper limit determined by radiation losses. The surface characterizations of the copper strip of the resonator by atomic force microscopy, low-energy electron diffraction, and scanning tunneling microscopy show that the surface is atomically clean, flat, and single crystalline. Measuring the ESR spectrum at 15K from a few nm thick molecular film of YPc2, we find a continuous-wave ESR sensitivity of 2.6 × 1011spins/G · Hz1/2, indicating that a signal-to-noise ratio of 3.9G · Hz1/2 is expected from a monolayer of YPc2 molecules. Advanced pulsed ESR experimental capabilities, including dynamical decoupling and electron-nuclear double resonance, are demonstrated using free radicals diluted in a glassy matrix.

The role of Cu doped Ba0.5Sr0.5Fe0.95Zr0.05O3-δ: Local structure distortion, conductivity, and magnetization

The composition Ba0.5Sr0.5Fe1-xCuxZr0.05O3-δ (BSFCZ-x, x = 0–0.20) was successfully synthesized by the sol-gel self-combustion method using citric acid as fuel combustion. Structure, local structure, electrical, and magnetic properties are investigated. The X-ray diffraction revealed the oxides exhibit a cubic structure (Pm3 m), and the lattice parameter increases with x. The X-ray absorption data are analyzed to determine the oxidation state of B site metal transition Fe and Cu through edge-energy E0 evaluation. Fe performs the oxidation states Fe3+ and Fe4+, similarly to Cu2+ and Cu3+. Furthermore, the pre-edge was analyzed to determine the spin state configuration of the 3d subshell. The local lattice distortion was evaluated through EXAFS, resulting in a distorted FeO6 octahedron elongated to the z-axis, inducing the Jahn-Teller effect. The nonstoichiometric δ-value (3-δ) measurement leads to oxygen vacancy VO⦁⦁ defect. The electrical conductivity of semiconducting behavior increases significantly after Cu is dissolved in BSFZ up to 60 S/cm at 500 °C, from initially 5 S/cm. Furthermore, the magnetic properties show a slight magnetic saturation Ms for BSFZ related to the low spin state configuration of Fe 3d subshell, then significantly increased on BSFCZ samples due to Cu provoking spin state dragged partly to high spin state configuration.