Spin crossover transition driven by pressure: Barocaloric applications

Abstract

This article describes a mean-field theoretical model for Spin-Crossover (SCO) materials and explores its implications. It is based on a simple Hamiltonian that yields the high spin molar fraction as a function of temperature and pressure, as well as a temperature-pressure phase diagram for the SCO transition. In order to test the model, we apply it to the giant Barocaloric Effect (BCE) of the SCO material [FeL$_2$][BF$_4$]$_2$ and comprehensively analyse its behavior. We found that optical phonons are responsible for 92\% of the total barocaloric entropy change. DFT calculations show that these optical phonons are mainly assigned to the low frequencies modes of vibration ($<400$ cm$^{-1}$), being associated to the Fe coordination.