Monte Carlo simulation of pressure-induced phase transitions in spin-crossover materials

Pressure-induced phase transitions of spin-crossover materials were simulated by a Monte Carlo simulation in the constant pressure ensemble for the first time. Here, as the origin of the cooperative interaction, we adopt elastic interaction among the distortions of the lattice due to the difference of the molecular sizes in different spin states, i.e., the high spin (HS) state and the low spin (LS) state. We studied how the temperature dependence of the ordering process changes with the pressure, and we obtained a standard sequence of temperature dependences that has been found in changing other parameters such as strength of the ligand field (S. Miyashita et al., Prog. Theor. Phys. \textbf{114}, 719 (2005)). Various effects of pressure on the spin-crossover ordering process are examined from a unified point of view.Comment: 5 pages, 6 figure

Multistability in an unusual phase diagram induced by the competition between antiferromagnetic-like short-range and ferromagnetic-like long-range interactions

The interplay between competing short-range (SR) and long-range (LR) interactions can cause nontrivial structures in phase diagrams. Recently, horn-shaped unusual structures were found by Monte Carlo simulations in the phase diagram of the Ising antiferromagnet (IA) with infinite-range ferromagnetic-like (F) interactions [Phys. Rev. B {\bf 93}, 064109 (2016); {\bf 96}, 174428 (2017)], and also in an IA with LR interactions of elastic origin modeling spin-crossover materials [Phys. Rev. B {\bf 96}, 144425 (2017)]. To clarify the nature of the phases associated with the horn structures, we study the phase diagram of the IA model with infinite-range F interactions by applying a variational free energy in a cluster mean-field (CMF) approximation. While the simple Bragg-Williams mean-field theory for each sublattice does not produce a horn structure, we find such structures with the CMF method. This confirms that the local thermal fluctuations enabled by the multisite clusters are essential for this phenomenon. We investigate in detail the structure of metastable phases in the phase diagram. In contrast to the phase diagram obtained by the Monte Carlo studies, we find a triple point, at which ferromagnetic-like, antiferromagnetic-like, and disordered phases coexist, and also six tristable regions accompanying the horn structure. We also point out that several characteristic endpoints of first-order transitions appear in the phase diagram. We propose three possible scenarios for the transitions related to the tristable regions. Finally, we discuss the relation between the triple point in this phase diagram and that of a possible lattice-gas model, in which solid, liquid, and gas phases can coexist.Comment: 28 pages, 11 figure

Simple Two-Dimensional Model for the Elastic Origin of Cooperativity among Spin States of Spin-Crossover Complexes

We study the origin of the cooperative nature of spin crossover (SC) between low spin (LS) and high spin (HS) states from the view point of elastic interactions among molecules. As the size of each molecule changes depending on its spin state, the elastic interaction among the lattice distortions provides the cooperative interaction of the spin states. We develop a simple model of SC with intra and intermolecular potentials which accounts for the elastic interaction including the effect of the inhomogeneity of the spin states, and apply constant temperature molecular dynamics based on the Nos\'e-Hoover formalism. We demonstrate that, with increase of the strength of the intermolecular interactions, the temperature dependence of the HS component changes from a gradual crossover to a first-order transition.Comment: 4 pages, 4 figure