Induced Spin Transitions Research Articles

Broadband transverse susceptibility in multiferroic Y-type hexaferrite Ba0.5Sr1.5Zn2Fe12O22

Noncollinear spin systems with magnetically induced ferroelectricity from changes in spiral magnetic ordering have attracted significant interest in recent research due to their remarkable magnetoelectric effects with promising applications. Single phase multiferroics are of great interest for these new multifunctional devices, being Y-type hexaferrites good candidates, and among them the ZnY compounds due to their ordered magnetic behaviour over room temperature. Polycrystalline Y type hexaferrites with composition Ba0.5Sr1.5Zn2Fe2O22 (BSZFO) were sintered in 1050 °C–1250 °C temperature range. Transverse susceptibility measurements carried out on these BSZFO samples in the temperature range 80–350 K with DC fields up to ± 5000 Oe reveal different behaviour depending on the sintering temperature. Sample sintered at 1250 °C is qualitatively different, suggesting a mixed Y and Z phase like CoY hexaferrites. Sintering at lower temperatures produce single phase Y-type, but the transverse susceptibility behaviour of the sample sintered at 1150 °C is shifted at temperatures 15 K higher. Regarding the DC field sweeps the observed behaviour is a peak that shifts to lower values with increasing temperature, and the samples corresponding to single Y phase exhibit several maxima and minima in the 250 K–330 K range at low DC applied field as a result of the magnetic field induced spin transitions in this compound.

Thermally Induced Spin Transition in a 2D Ferrous Nitroprusside

This study reports the intercalation of pyridine molecules between neighboring layers of two‐dimensional (2D) ferrous nitroprusside. In the material under study, the stacking of neighboring layers results in the formation of a long range ordered solid, where the 3D structure is supported by dipole‐dipole attractive interactions between neighboring pyridine molecules in the interlayer region. No chemical interactions were observed between layers, which preserve their identity as a 2D material. In this hybrid inorganic–organic solid, a thermal induced spin transitions from high to low spin on cooling and then from low to high spin on heating were observed. Such thermal induced spin crossover transition takes place with a pronounced hysteresis of 18 K, according to the magnetic and DSC measurements. That spin crossover transition is characterized by an extremely small structural change, involved a unit cell volume reduction from the high to low spin states of only 0.7 % and a related Fe–NPyridine distance shortening of 0.10 Å. The two spin states and the transition between them were additionally characterized from magnetic and DSC data and, Raman and Mössbauer spectra.

Bias induced spin transitions of spin crossover molecules: the role of charging effect.

The spin transition of spin crossover molecules induced by bias voltages from low spin to high spin was observed recently and several mechanisms were suggested to understand it. However, these mechanisms fail to explain the dependence of spin transitions on the bias polarity in experiments and thus may still be questionable. Based on a first-principles study, we propose that the bias-induced spin transition is triggered by a charging effect, namely, the filling of the lowest unoccupied molecular orbital of spin crossover molecules. Our proposal is substantiated by three steps: (1) the spin transition from low spin to high spin can be achieved by charging the isolated spin crossover molecules with one extra electron; (2) in molecular junctions, the charging of spin crossover molecules can be realized by electron transfer from electrodes to molecules under finite bias; (3) more importantly, the electron transfer is dependent on the bias polarity due to asymmetrical couplings of the sandwiched molecule with two electrodes. This mechanism satisfactorily explains the bias-polarity dependent spin transitions in experiments [Miyamachi et al., Nat. Commun., 2012, 3, 938; Gopakumar et al., Angew. Chem. Int. Ed., 2012, 51, 6262].

Protecting a solid-state spin from decoherence using dressed spin states.

We report experimental studies of dressing an electron spin in diamond with resonant and continuous microwave fields to protect the electron spin from magnetic fluctuations induced by the nuclear spin bath. We use optical coherent population trapping (CPT) to probe the energy level structure, optically induced spin transitions, and spin decoherence rates of the dressed spin states. Dressing an electron spin with resonant microwaves at a coupling rate near 1MHz leads to a 50 times reduction in the linewidth of the spin transition underlying the CPT process, limited by transit-time broadening. Compared with dynamical decoupling, where effects of the bath are averaged out at specific times, the dressed spin state provides a continuous protection from decoherence.

Direct high-precision measurement of the magnetic moment of the proton

One of the fundamental properties of the proton is its magnetic moment, µp. So far µp has been measured only indirectly, by analysing the spectrum of an atomic hydrogen maser in a magnetic field. Here we report the direct high-precision measurement of the magnetic moment of a single proton using the double Penning-trap technique. We drive proton-spin quantum jumps by a magnetic radio-frequency field in a Penning trap with a homogeneous magnetic field. The induced spin transitions are detected in a second trap with a strong superimposed magnetic inhomogeneity. This enables the measurement of the spin-flip probability as a function of the drive frequency. In each measurement the proton's cyclotron frequency is used to determine the magnetic field of the trap. From the normalized resonance curve, we extract the particle's magnetic moment in terms of the nuclear magneton: μp = 2.792847350(9)μN. This measurement outperforms previous Penning-trap measurements in terms of precision by a factor of about 760. It improves the precision of the forty-year-old indirect measurement, in which significant theoretical bound state corrections were required to obtain µp, by a factor of 3. By application of this method to the antiproton magnetic moment, the fractional precision of the recently reported value can be improved by a factor of at least 1,000. Combined with the present result, this will provide a stringent test of matter/antimatter symmetry with baryons.

Pressure and temperature induced high spin–low spin phase transition: Macroscopic and microscopic consideration

The behavior under pressure of the high spin–low spin phase transition in the coordination compounds containing 3d ions is analyzed using thermodynamic and microscopic approaches. For thermodynamic approach the mean field model with interactions between spin-crossover molecules is considered. Microscopic model takes into account the interaction of d electrons of the transition metal ions with full symmetric distortions of the ligands. The relationship of the thermodynamic interaction parameters with microscopic ones is installed and shown how the quantum–mechanical interactions form the cooperativity of the system. Within the microscopic model the temperature and pressure dependences of the high spin fraction in 2-D compounds {Fe(3-Fpy)2[M(CN)4]} (M=Pd, Pt) are simulated and microscopic parameters are evaluated. It is concluded that different experimental behaviors of the temperature and pressure induced spin transitions are determined by different variations of the inelastic and elastic energies under pressure, and vibrational component of the free energy drives the ST equally with electronic part.

Observation of Spin Flips with a Single Trapped Proton

Radio-frequency induced spin transitions of one individual proton are observed. The spin quantum jumps are detected via the continuous Stern-Gerlach effect, which is used in an experiment with a single proton stored in a cryogenic Penning trap. This is an important milestone towards a direct high-precision measurement of the magnetic moment of the proton and a new test of the matter-antimatter symmetry in the baryon sector.

Pressure-Induced Cooperative Spin Transition in Iron(II) 2D Coordination Polymers: Room-Temperature Visible Spectroscopic Study

For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously reported for thermally induced spin transition at constant pressure for the title compounds (Chem.-Eur. J.2009, 15, 10960). Relevance of the elastic energy, Δ(elast), as a corrective parameter accounting for the pressure dependence of the critical temperature of thermally induced spin transitions (Clausius-Clapeiron equation) is also demonstrated and discussed.

Controlled Intramolecular Electron Transfers in Cyanide-Bridged Molecular Squares by Chemical Modifications and External Stimuli

A series of cyanide bridged Fe-Co molecular squares, [Co(2)Fe(2)(CN)(6)(tp*)(2)(dtbbpy)(4)](PF(6))(2)·2MeOH (1), [Co(2)Fe(2)(CN)(6)(tp*)(2)(bpy)(4)](PF(6))(2)·2MeOH (2), and [Co(2)Fe(2)(CN)(6)(tp)(2)(dtbbpy)(4)](PF(6))(2)·4H(2)O (3) (tp = hydrotris(pyrazol-1-yl)borate, tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate, bpy =2,2'-bipyridine, dtbbpy =4,4'-di-tert-butyl-2,2'-bipyridine), were prepared by the reactions of [Fe(CN)(3)(L)](-) (L = tp or tp*) with Co(2+) and bidentate ligands (bpy or dtbbpy) in MeOH. In the molecular squares, Fe and Co ions are alternately bridged by cyanide ions, forming macrocyclic tetranuclear cores. Variable temperature X-ray structural analyses and magnetic susceptibility measurements confirmed that 1 exhibits two-step charge-transfer induced spin transitions (CTIST) centered at T(1/2) = 275 and 310 K in the solid state. The Fe and Co ions in 1 are the low-spin (LS) Fe(III) and high-spin (HS) Co(II) ions, described here in the high-temperature (HT) phase ([Fe(III)(LS2)Co(II)(HS2)]) at 330 K, while a low-temperature (LT) phase ([Fe(II)(LS2)Co(III)(LS2)]) with LS Fe(II) and Co(III) ions was dominant below 260 K. X-ray structural analysis revealed that in the intermediate (IM) phase at 298 K 1 exhibits positional ordering of [Fe(III)(LS2)Co(II)(HS2)] and [Fe(II)(LS2)Co(III)(LS2)] species with the 2:2 ratio. In photomagnetic experiments on 1, light-induced CTIST from the LT to the HT phase was observed by excitation of Fe(II) → Co(III) intervalence charge transfer (IVCT) band at 5 K and the trapped HT phase thermally relaxed to the LT phase in a two-step fashion. On the other hand, 2 and 3 are in the HT and LT phases, respectively, throughout the entire temperature range measured, and no CTIST was observed. UV-vis-NIR absorption spectral measurements and cyclic voltammetry in solution revealed that the different electronic states in 1-3 are ascribable to the destabilization of iron and cobalt ion d-orbitals by the introduction of methyl and tert-butyl groups to the ligands tp and bpy, respectively. Temperature dependence of UV-vis-NIR spectra confirmed that 1 exhibited a one-step CTIST in butyronitrile, of which T(1/2) varied from 227 to 280 K upon the addition of trifluoroacetic acid.

XAS at the materials science X-ray beamline BL8 at the DELTA storage ring

The hard X-ray beamline BL 8 at the 1.5 GeV electron storage ring DELTA is described, and experimental data of different fields of research are presented. Making use of the intense X-ray beam emitted by a superconducting wiggler, the beamline is dedicated to X-ray absorption experiments. Three different monochromator crystal pairs are permanently available for experiments in the spectral range from about 1 keV to ca. 25 keV photon energy. Results of reference materials show that high quality EXAFS data can be obtained using Si(111) and Si(311) monochromators. First measurements in the energy range between 1.2 and 5 keV have been accomplished using YB66(400) monochromator crystals. The experimental hutch accommodates a unique 6-axis diffractometer which is well suited for all kinds of diffraction and absorption experiments, including the grazing incidence geometry. The diffractometer can carry heavy loads related to non-ambient sample environments such as e.g. ultrahigh vacuum sample stages or cryostats. Here we present typical results obtained at BL8 in different areas of materials science including investigations of dilute alloys by fluorescence mode EXAFS and the study of the structural changes associated with temperature induced spin transitions of metallo-supramolecular polyelectrolyte-amphiphile-complexes.

Theoretical Description of the Structure and Magnetic Properties of Nitroxide−Cu(II)−Nitroxide Spin Triads by Means of Multiconfigurational Ab Initio Calculations

The structural, electronic and magnetic properties of two different models of the heterospin polymer chain complexes of Cu2+ hexafluoroacetylacetonate with two pyrazole-substituted nitronyl nitroxides Cu(hfac)2L(R) have been studied by means of multiconfigurational perturbation theory based on a CASSCF (complete active space self-consistent field) wave function, i.e. the CASPT2 method. Our calculations reveal the presence of two minima in the electronic energy curve along the Cu-O(L) bond, separated by only 6 kcal/mol, and corresponding to the X-ray structures of the CuO6 centers in Cu(hfac)2L(Pr) at 115 and 293 K, respectively. The two energetic minima are characterized by a different electronic structure, thus giving rise to a different three-spin exchange coupling and explaining the thermally induced spin transitions in this family of compounds. The concomitant variations in the magnetic properties, i.e. g factors and magnetic moments mu(eff)(T) were calculated and compared with the experimental data of Cu(hfac)2L(Pr). Even if the correspondence is only qualitative, our calculations provide a convincing explanation of the observed magnetic peculiarities. In particular, at low temperatures, the predicted ground-state is 2A(u), well separated from the 2A(g), 4A(u) states and therefore exclusively populated. Its calculated g factors, g(parallel) = 1.848, g(perpendicular) = 1.965, 1.974, qualitatively correspond to the observed g < 2 signals in the low-temperature EPR spectra. The previously assumed formal spin assignment >N-O*-Cu-*O-N < for these linear spin triads is challenged by our calculations, pointing instead to a more important role of the end-standing NO in the exchange interactions with Cu(II).

Isoequilibrium relationships and cooperative effects in spin-state transitions in solution

Abstract Thermal induced spin transitions between low- and high-spin states of Fe(II) complexes are commonly observed in the solid state. Cooperative effects, such as abrupt and two-step spin crossover, are typical for these objects and arise from intermolecular interactions described by several formalisms. These phenomena appear as deviations from the linearity of the respective van't Hoff plots. In solutions, molecular interactions manifest themselves in isoequilibrium relationships (IERs) as well as in a few cases of specific deviations of van't Hoff plots from linearity. The nature of these phenomena will be discussed on the basis of a statistical-thermodynamic model of spin crossover.

Thermally Induced Spin Transitions in Nitroxide−Copper(II)−Nitroxide Spin Triads Studied by EPR

Thermally induced spin transitions in a family of heterospin polymer chain complexes of Cu2+ hexafluoroacetylacetonate with two pyrazole-substituted nitronyl nitroxides are studied using electron paramagnetic resonance (EPR) spectroscopy. The structural rearrangements at low temperatures induce spin transitions in exchange-coupled spin triads of nitroxide-copper(II)-nitroxide. The values of exchange interactions in spin triads of studied systems are typically on the order of tens to hundreds of inverse centimeters. The large magnitude of exchange interaction determines the specific and very informative peculiarities in EPR spectra due to the predominant population of the ground state of a spin triad and spin exchange processes. The variety of these manifestations depending on structure and magnetic properties of spin triads are described. EPR is demonstrated as an efficient tool for the characterization of spin transitions and for obtaining information on the temperature-dependent sign and value of the exchange interaction in strongly coupled spin triads.

Coherent Control of a Single Electron Spin with Electric Fields

Manipulation of single spins is essential for spin-based quantum information processing. Electrical control instead of magnetic control is particularly appealing for this purpose, because electric fields are easy to generate locally on-chip. We experimentally realized coherent control of a single-electron spin in a quantum dot using an oscillating electric field generated by a local gate. The electric field induced coherent transitions (Rabi oscillations) between spin-up and spin-down with 90 degrees rotations as fast as approximately 55 nanoseconds. Our analysis indicated that the electrically induced spin transitions were mediated by the spin-orbit interaction. Taken together with the recently demonstrated coherent exchange of two neighboring spins, our results establish the feasibility of fully electrical manipulation of spin qubits.

Microwave electric field induced spin transitions of AlAs 2D electrons

We present the first direct electron spin resonance (ESR) on a 2D electron gas in a III – V semiconductor. ESR on a high mobility 2D electron gas in a single AlAs quantum well reveals an electronic g -factor of 1.991 at 9.35 GHz and 1.989 at 34 GHz with a minimal linewidth of 7 Gauss. Both the signal amplitude and its dependence on the position and orientation of the sample in the cavity unambiguously demonstrate that the spin transitions in our experiment are caused by the microwave electric field. We present a model that ascribes the spin transitions to the effective magnetic field acting on the electron spins that arises from (Bychkov–Rashba) spin-orbit interaction and the modulation of the electron wavevector around k F induced by the microwave electric field.

Field induced spin transitions and large magnetoresistance in the quasi-one-dimensional magnet Ca 3Co 2O 6

Magnetic and magnetoresistance effect of needle shaped crystal and slightly Co rich Ca 3Co 2O 6 was investigated in a temperature range between 2 and 100 K and in a dc magnetic field range less than 7 T and in pulsed fields less than 20 T. We found 1/3 m s and 2/3 m s plateaus of the magnetization for the full magnetization m s and large negative magnetoresistance effect of 10% at the same magnetic fields, respectively.

Solid solutions: An efficient way to control the temperature of spin transition in heterospin crystals MxCu1−x(hfac)2L (M=Mn, Ni, Co; L=nitronyl nitroxide)

Abstract A series of mixed-metal solid solutions MxCu1 − x(hfac)2L (M = Mn, Ni, and Co) liable to undergo thermally induced spin transitions have been synthesized. The structure and magnetic properties of the compounds have been investigated. By varying the metal to be incorporated in the complex (Mn, Ni, or Co) and the value of x, one can control the character of the magnetic anomaly.

A novel Fe(II) framework structure: correlations to its thermal and light induced spin transitions

A novel Fe(II) framework structure: correlations to its thermal and light induced spin transitions

Unusual spin transitions

New heterospin complexes of Cu(hfac)2 (hfac, hexafluoroacetylacetonate) with pyrazole-substituted nitronyl nitroxides have been found that in the solid state exhibit thermally induced spin transitions analogous to spin crossover. For the first complex, [Cu(hfac)2Li-Pr], at room temperature, the Cu—OL distances, where OL is the oxygen atom of the nitroxyl group, are very short (2.143 Å). This leads to a strong antiferromagnetic exchange (∼-120cm−1) in the > N—·O—Cu2+—O·—N < exchange clusters. The CuO6 coordination units formed by four O atoms of the two hfac anions and by the nitroxyl O atoms of the two bridging nitroxides have a rare form of flattened octahedra, transformed at low temperatures into elongated octahedra with shorter Cu—OL distances (2.143 Å→2.002Å) and two longer Cu—Ohfac distances (2.130 Å→2.293 Å). For the second complex, [Cu(hfac)2LBu·0.5C6H14], unusual low temperature structural dynamics of heterospin systems have been found. It is characterized by the formation of two types of CuO6 unit. The axial Cu—OL distances are lengthened in one unit (2.250 Å→2.347 Å) and shortened in the other (2.250 Å → 2.006 Å). This leads to a sophisticated μeff(T) dependence with μeff drastically decreased at 163 K as a result of full coupling of two spins in half of all >N—·O—Cu2+—O·—N < exchange clusters and to a shift from antiferromagnetic to ferromagnetic exchange in the other half.

Nonclassical Spin Transitions

A family of heterospin polymer chain complexes Cu(hfac)2 with pyrazole-substituted nitronyl nitroxides (LR, where R = Me, Et, Pr) of the composition Cu(hfac)2LR was found. In the solid state the complexes undergo low-temperature structural rearrangements accompanied by magnetic effects analogous to spin-crossover. Polymer chains with a “head-to-head” or “head-to-tail” motif in Cu(hfac)2LR are formed as a result of the bridging coordination of LR through the imine N atom of pyrazole and one of the O atoms of the nitronyl nitroxide fragment. Despite the low-temperature structural phase transition, the single crystals retain the quality needed for an X-ray investigation, due to which the compounds may be studied at different temperatures and structural dynamics studies are possible. It was found that the major structural changes mainly occur in the coordination polyhedra, leading to phenomena analogous to spin-crossover. This rearrangement is possible due to the Jahn–Teller nature of the Cu(II) ion, which is responsible for the pulled octahedron structure of the coordination unit. The transition of the coordinated nitroxyl O atoms from the axial (dCu–O ∼ 2.2-2.4 A) to equatorial (dCu–O ∼ 2.0 A) position is accompanied by a transition of the exchange interaction in the Cu(II)–O•–N< exchange clusters from weak ferromagnetic (or weak antiferromagnetic) to strong anti-ferromagnetic, compensating the spins of the Cu(II) ion and the nitroxyl fragment. The motif of the polymer chain (“head-to-head” or “head-to-tail”) proved to be inessential to the occurrence of thermally induced spin transitions. In both cases, the shortening of the Cu–O distance in the Cu(II)–O•–N< exchange cluster decreases the effective magnetic moment of the complex by a factor of \(\sqrt 2 \), because spin compensation occurs in only half of all coordination units (Cu(hfac)2LPr, Cu(hfac)2LMe, and Cu2(hfac)4LMeLEt). The low-temperature structural rearrangement in Cu(hfac)2LEt is unusual; it leads to longer Cu–O distances in the Cu(II)–O•–N< exchange cluster and to an abrupt transition from antiferromagnetic to ferromagnetic exchange. At reduced temperatures, the unit cell volume decreased by 5-6% in all of the compounds. The cell parameters are large and so is the absolute value of the decrease (up to 400 A3). The maximal decrease in the cell dimensions was observed in the directions of the chains and in the directions of the maximal shortening of the Cu...Cu distances. Minimal compression or even extension of the cell took place in the direction of lengthening of the Cu–Ohfac distances. The single crystals of Cu(hfac)2LEt and Cu(hfac)2LPr possess high mechanical stability in repeated cooling-heating cycles.