Atomistic description of spin crossover under pressure and its giant barocaloric effect

The pressure-dependent evolution of the Spin Crossover (SCO) transition has garnered significant interest due to its connection to the giant barocaloric effect (BCE) near room temperature. Pressure alters both the molecular and solid-state structures of SCO materials, affecting the relative stabilit...

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Detalles Bibliográficos
Autores: Vela, Sergi, Ribas-Arino, Jordi, Vallone, Steven P., dos Santos, António M., Halcrow, Malcolm A., Sandeman, Karl G.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/402281
Acceso en línea:http://hdl.handle.net/10261/402281
https://api.elsevier.com/content/abstract/scopus_id/105017749918
Access Level:acceso abierto
Palabra clave:Spin Crossover (SCO)
SCO materials
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Descripción
Sumario:The pressure-dependent evolution of the Spin Crossover (SCO) transition has garnered significant interest due to its connection to the giant barocaloric effect (BCE) near room temperature. Pressure alters both the molecular and solid-state structures of SCO materials, affecting the relative stability of low- and high-spin states and, consequently, the transition temperature (T<inf>1/2</inf>). Crucially, the shape of the T<inf>1/2</inf>vs. pressure curve dictates the magnitude of the BCE, making its accurate characterization essential for identifying high-performance materials. In this work, we investigate the nonlinear T<inf>1/2</inf>vs. pressure behavior of the prototypical SCO complex [FeL<inf>2</inf>][BF<inf>4</inf>]<inf>2</inf> [L = 2,6-di(pyrazol-1-yl)pyridine] using solid-state PBE+U computations. Our results unveil the mechanisms by which pressure influences its SCO transition, including the onset of a phase transition, as well as the key role of low-frequency phonons in the BCE. Furthermore, we establish a computational protocol for accurately modeling the BCE in SCO crystals, providing a powerful tool for the rapid and efficient discovery of new materials with enhanced barocaloric performance.