Pressure-induced Jahn-Teller suppression in Rb2CuCl4( H2O )2: Pseudo-Jahn-Teller effect
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AuthorAguado Menéndez, Fernando; Rodríguez González, Fernando; Valiente Barroso, Rafael; Itié, Jean Paul; Munsch, Pascal
In this work we investigate the variation of the local structure around Cu2+ as well as the crystal structure in Rb2CuCl4(H2O)2 through x-ray absorption spectroscopy (XAS) and x-ray diffraction (XRD) as a function of pressure. We show that the application of pressure induces a local structural change in the Jahn-Teller (JT) CuCl4(H2O)22− complex from an axially elongated complex to a compressed one, yielding disappearance of the JT distortion related to the four in-plane Cl− ligands, which are responsible for the antiferrodistortive structure displayed by the crystal at ambient pressure. According to the Pseudo-Jahn-Teller (PJT) theory (electron-phonon coupling E⊗e), the presence of water ligands enhances the JT release at pressures well below the metallization pressure. The results are compared with recent pressure experiments on A2CuCl4 layered perovskites and heteronuclear CuCl4L2 complex series, L :Cl→H2O→NH3, and explained on the basis of the PJT model.
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