Intrinsic effects of the boundary condition on switching processes in spin-crossover solids

We investigated domain growth in switching processes between the low-spin and high-spin phases in thermally induced hysteresis loops of spin-crossover (SC) solids. Elastic interactions among the molecules induce effective long-range interactions, and thus the boundary condition plays a significant role in the dynamics. In contrast to SC systems with periodic boundary conditions, where uniform configurations are maintained during the switching process, we found that domain structures appear with open boundary conditions. Unlike Ising-like models with short-range interactions, domains always grow from the corners of the system. The present clustering mechanism provides an insight into the switching dynamics of SC solids, in particular, in nano-scale systems.Comment: 5pages, 5figure

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

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

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