Hidden Devil's staircase in a two-dimensional elastic model of spin crossover materials

TL;DR

This paper models spin crossover materials using an elastic lattice mapped to a long-range Ising model, revealing a complex Devil's staircase phenomenon in spin state ordering influenced by elastic frustration and material parameters.

Contribution

It provides a microscopic derivation of the Ising model for SCO materials and demonstrates the emergence of a Devil's staircase in spin ordering due to elastic interactions.

Findings

Large number of spin-state orderings observed

Devil's staircase behavior confirmed in model simulations

Experimental relevance to framework materials like Fe-based compounds

Abstract

Spin crossover (SCO) materials are reversible molecular switches found in a wide range of transition metal complexes and metal organic frameworks (MOFs). They exhibit diverse spin state orderings and transitions between them. We present an exact mapping from an elastic lattice mismatch model to a long-range Ising model, with an inverse square decay of the interaction strengths at large distances (on the square lattice). This provides a microscopic justification for an Ising model description, which has previously only been justified on phenomenological grounds. Elastic frustration is required for non-zero Ising interactions, but whether or not the short-range interactions in the Ising model are geometrically frustrated depends on the ratio of the bulk and shear moduli or equivalently Poisson's ratio. We show that, for a simple square lattice model with realistic parameters, sweeping the enthalpy difference between the two spin-states at zero temperature leads to a large (probably infinite) number of spin-state orderings and corresponding steps in the fraction of high-spin ions, consistent with a Devil's staircase. The staircase can also be climbed by varying the temperature, but then some of the steps are hidden and only a finite number remain, consistent with experiments on relevant framework materials, such as {(Fe[Hg(SCN)$_3$]$_2$(4,4'-bipy)$_2$)}$_n$. Our results are also relevant to other binary systems with lattice mismatch, e.g., heterogeneous solids.