Sb-5s lone pair dynamics and collinear magnetic ordering in Ba2FeSbSe5

TL;DR

This study investigates the local and average crystal structures of Ba2FeSbSe5, revealing Sb-5s lone pair dynamics influence local structure deviations, and identifies collinear magnetic ordering below 58 K with specific exchange interactions.

Contribution

It provides new insights into the role of Sb-5s lone pair dynamics in local structure deviations and details the collinear magnetic ordering in Ba2FeSbSe5.

Findings

Local structure deviations are due to Sb-5s lone pair dynamics.

Below 58 K, Fe3+ spins order collinearly with specific exchange interactions.

Nearest-neighbor interactions are antiferromagnetic, next-nearest are ferromagnetic.

Abstract

Neutron diffraction and X-ray pair distribution function (XPDF) experiments were performed in order to investigate the magnetic and local crystal structures of Ba2FeSbSe5 and to compare them to the average (i.e. long-range) structural model, previously obtained by single crystal X-ray diffraction. Changes in the local crystal structure (i.e. in the second coordination sphere) are observed upon cooling from 295 K to 95 K resulting in deviations from the average (i.e. long-range) crystal structure. This work demonstrates, that these observations cannot be explained by local or long-range magnetoelastic effects involving Fe-Fe correlations. Instead, we found, that the observed differences between local and average crystal structure can be explained by Sb-5s lone pair dynamics. We also find, that below the N\'eel temperature (TN = 58 K), the two distinct magnetic Fe3+ sites order collinearly, such that a combination of antiparallel and parallel spin arrangements along the b-axis results. The nearest-neighbor arrangement (J1 = 6 {\AA}) is fully antiferromagnetic, while next-nearest-neighbor interactions are ferromagnetic in nature.