Spin canting and ferromagnetism in a AuFe alloy: Mössbauer and magnetic measurements

We have made Mössbauer polarization and susceptibility measurements above technical saturation on Au-19 at.% Fe. Just below the magnetic ordering temperature the system behaves as a ferromagnet, but random local canting sets in at lower temperatures. A well-defined canting transition temperature cannot be established from the data, but canting begins above the temperature at which the low-field susceptibility shows a sharp falloff

Structure of Metastable States in Phase Transitions with High-Spin Low-Spin Degree of Freedom

Difference of degeneracy of the low-spin (LS) and high-spin (HS) states causes interesting entropy effects on spin-crossover phase transitions and charge transfer phase transitions in materials composed of the spin-crossover atoms. Mechanisms of the spin-crossover (SC) phase transitions have been studied by using Wajnflasz model, where the degeneracy of the spin states (HS or LS) is taken into account and cooperative natures of the spin-crossover phase transitions have been well described. Recently, a charge transfer (CT) phase transition due to electron hopping between LS and HS sites has been studied by using a generalized Wajnflasz model. In the both systems of SC and CT, the systems have a high temperature structure (HT) and a low temperature structure (LT), and the change between them can be a smooth crossover or a discontinuous first order phase transition depending on the parameters of the systems. Although apparently the standard SC system and the CT system are very different, it is shown that both models are equivalent under a certain transformation of variables. In both systems, the structure of metastable state at low temperatures is a matter of interest. We study temperature dependence of fraction of HT systematically in a unified model, and find several structures of equilibrium and metastable states of the model as functions of system parameters. In particular, we find a reentrant type metastable branch of HT in a low temperature region, which would play an important role to study the photo-irradiated processes of related materials.Comment: 19 pages, 11 figure

A Unified Theoretical Description of the Thermodynamical Properties of Spin Crossover with Magnetic Interactions

After the discovery of the phenomena of light-induced excited spin state trapping (LIESST), the functional properties of metal complexes have been studied intensively. Among them, cooperative phenomena involving low spin-high spin (spin-crossover) transition and magnetic ordering have attracted interests, and it has become necessary to formulate a unified description of both phenomena. In this work, we propose a model in which they can be treated simultaneously by extending the Wajnflasz-Pick model including a magnetic interaction. We found that this new model is equivalent to Blume-Emery-Griffiths (BEG) Hamiltonian with degenerate levels. This model provides a unified description of the thermodynamic properties associated with various types of systems, such as spin-crossover (SC) solids and Prussian blue analogues (PBA). Here, the high spin fraction and the magnetization are the order parameters describing the cooperative phenomena of the model. We present several typical temperature dependences of the order parameters and we determine the phase diagram of the system using the mean-field theory and Monte Carlo simulations. We found that the magnetic interaction drives the SC transition leading to re-entrant magnetic and first-order SC transitions.Comment: 30pages, 11figure

Size dependence of the photoinduced magnetism and long-range ordering in Prussian blue analog nanoparticles of rubidium cobalt hexacyanoferrate

Nanoparticles of rubidium cobalt hexacyanoferrate (Rb$_j$Co$_k$[Fe(CN)$_6$]$_l \cdot n$H$_2$O) were synthesized using different concentrations of the polyvinylpyrrolidone (PVP) to produce four different batches of particles with characteristic diameters ranging from 3 to 13 nm. Upon illumination with white light at 5 K, the magnetization of these particles increases. The long-range ferrimagnetic ordering temperatures and the coercive fields evolve with nanoparticle size. At 2 K, particles with diameters less than approximately 10 nm provide a Curie-like magnetic signal.Comment: 10 pages, 6 figures in text, expanded text and dat

Dynamical Ising-like model for the two-step spin-crossover systems

In order to reproduce the two-step relaxation observed experimentally in spin-crossover systems, we investigate analytically the static and the dynamic properties of a two-sublattice Ising-like Hamiltonian. The formalism is based on a stochastic master equation approach. It is solved in the mean-field approximation, and yields two coupled differential equations that correspond to the HS fractions of the sublattices A and [email protected] ; [email protected]

Magnetization steps in a diluted Heisenberg antiferromagnetic chain: Theory and experiments on TMMC:Cd

A theory for the equilibrium low-temperature magnetization M of a diluted Heisenberg antiferromagnetic chain is presented. The magnetization curve, M versus B, is calculated using the exact contributions of finite chains with 1 to 5 spins, and the "rise and ramp approximation" for longer chains. Some non-equilibrium effects that occur in a rapidly changing B, are also considered. Specific non-equilibrium models based on earlier treatments of the phonon bottleneck, and of spin flips associated with cross relaxation and with level crossings, are discussed. Magnetization data on powders of TMMC diluted with cadmium [i.e., (CH_3)_4NMn_xCd_(1-x)Cl_3, with 0.16<=x<=0.50 were measured at 0.55 K in 18 T superconducting magnets. The field B_1 at the first MST from pairs is used to determine the NN exchange constant, J, which changes from -5.9 K to -6.5 K as x increases from 0.16 to 0.50. The magnetization curves obtained in the superconducting magnets are compared with simulations based on the equilibrium theory. Data for the differential susceptibility, dM/dB, were taken in pulsed magnetic fields (7.4 ms duration) up to 50 T, with the powder samples in a 1.5 K liquid-helium bath. Non-equilibrium effects, which became more severe as x decreased, were observed. The non-equilibrium effects are tentatively interpreted using the "Inadequate Heat Flow Scenario," or to cross-relaxation, and crossings of energy levels, including those of excited states.Comment: 16 pages, 14 figure

Equivalence between non-bilinear spin-SS Ising model and Wajnflasz model

We propose the mapping of polynomial of degree 2S constructed as a linear combination of powers of spin-$S$ (for simplicity, we called as spin-$S$ polynomial) onto spin-crossover state. The spin-$S$ polynomial in general can be projected onto non-symmetric degenerated spin up (high-spin) and spin down (low-spin) momenta. The total number of mapping for each general spin-$S$ is given by $2(2^{2S}-1)$. As an application of this mapping, we consider a general non-bilinear spin-$S$ Ising model which can be transformed onto spin-crossover described by Wajnflasz model. Using a further transformation we obtain the partition function of the effective spin-1/2 Ising model, making a suitable mapping the non-symmetric contribution leads us to a spin-1/2 Ising model with a fixed external magnetic field, which in general cannot be solved exactly. However, for a particular case of non-bilinear spin-$S$ Ising model could become equivalent to an exactly solvable Ising model. The transformed Ising model exhibits a residual entropy, then it should be understood also as a frustrated spin model, due to competing parameters coupling of the non-bilinear spin-$S$ Ising model

Towards controlling the solid state valence tautomeric interconversion character by solvation

Crystals of [Co<i>(diox)</i>₂­(4-NO₂-py)₂] (<b>1</b>) and [Co<i>(diox)</i>₂­(4-CN-py)₂] (<b>2</b>) where <i>diox</i> are the <i>o</i>-dioxolene 3,5-di-<i>t</i>-butylsemiquinonate (SQ^•–) and/or 3,5-di-<i>t</i>-butylcatecholate (Cat^2–) ions, 4-NO₂-py is 4-nitro-pyridine, 4-CN-py is 4-cyano-pyridine, are among the few known crystals presenting both thermally induced and photoinduced <i>ls</i>-[M⁺³(SQ^•–)­(Cat^2–)] ↔ <i>hs</i>-[M²⁺(SQ^•–)₂] valence tautomeric interconversion (VTI). In <b>2</b>, the thermal-induced VTI is cooperative, characterizing an abrupt conversion, and in <b>1</b> it is noncooperative. In this work, crystals of [Co<i>(diox)</i>₂­(4-NO₂-py)₂]­·benzene (<b>1BZ</b>), [Co<i>(diox)</i>₂­(4-NO₂-py)₂]­·toluene (<b>1TL</b>), [Co<i>(diox)</i>₂­(4-CN-py)₂]­·benzene (<b>2BZ</b>), and [Co<i>(diox)</i>₂­(4-CN-py)₂]­·toluene (<b>2TL</b>) have been prepared and analyzed by single crystal X-ray diffraction in order to investigate how solvation modulates thermally induced VTI. Crystallographic data were also successfully used together with the two-state equilibrium equation to estimate Δ<i>H</i>° and Δ<i>S</i>° VTI thermodynamic parameters. The solvate crystals, like the nonsolvated ones, present essentially reversible thermally induced VTI. The <b>1TL</b> crystal presents the same monoclinic symmetry and the same intermolecular hydrogen-bonded network of <b>1</b>, and both present a noncooperative thermal-induced VTI. The <b>1BZ</b> crystal has triclinic symmetry and presents a cooperative VTI with a thermal hysteresis of ∼30 K. In contrast to <b>2</b>, thermally induced VTI in <b>2BZ</b> and <b>2TL</b> is noncooperative despite the fact that <b>2</b>, <b>2BZ</b>, and <b>2TL</b> crystals exhibit the same monoclinic symmetry and the same intermolecular hydrogen-bonded network. In <b>2BZ</b> and <b>2TL</b> benzene and toluene molecules as well as the <i>t</i>-butyl groups of the <i>o</i>-dioxolene molecules convert gradually from being dynamically disordered at about 300 K to a static disorder state below 150 K. The layer separation distance of interacting [Co<i>(diox)</i>₂­(4-X-py)₂], X = CN and NO₂, molecules in all solvate crystals is ∼15 Å, whereas in <b>2</b>, which presents cooperative VTI, it is ∼12 Å. An order–disorder component might account for the stabilization of the metastable <i>hs</i>-Co²⁺ state in <b>2BZ</b> and in <b>2TL</b>, but no disorder was found in the <b>1TL</b> crystals. Therefore, the lack of cooperativity in the thermally induced VTI in these crystals seems to be due to the large distance between the layers of interacting molecules. Cooperativity in the VTI of <b>1BZ</b> crystal is likely to be related with the unique molecular bond scheme network that connects neighboring active [Co<i>(diox)</i>₂­(4-NO₂-py)₂] molecules through the <i>o</i>-dioxolene oxygen atoms bonded directly to the Co ion

Spectral sensitive phonon wipeout due to a fluctuating spin state in a Fe2+ coordination polymer

Raman scattering in the spin-crossover system [Fe(pmd)(H2O){Au(CN)2}2]*H2O reveals a complex three-phase spin-state transition in contrast to earlier observations in magnetization measurements. We observe different spin state phases as function of temperature and electromagnetic radiation in the visible spectral range. There exists a fluctuating spin state phase with an unexpected wipeout of the low frequency phonon scattering intensity. Furthermore we observe one phase with reduced symmetry that is attributed to a cooperative Jahn-Teller effect. Pronounced electron-phonon interaction manifests itself as a strong Fano-resonance of phonons related to {FeN6} and {FeN4O2} coordination octahedra. Density functional theory supports this interpretation.Comment: 9 pages, 9 figures, 3 table