Optical anisotropy and electronic states in the pleochroic material Ca$_3$ReO$_5$Cl$_2$

Abstract

Pleochroism is a type of optical anisotropy in which the apparent color of a material varies depending on the polarization and propagation direction of incident light. The oxychloride compound Ca$_3$ReO$_5$Cl$_2$ has recently attracted attention due to its pronounced pleochroism. The paramagnetic state of this compound, characterized by localized Re 5$d$ electrons, is challenging to describe within conventional first-principles methods. In this study, we investigate the optical anisotropy in Ca$_3$ReO$_5$Cl$_2$ using first-principles calculations, with particular focus on the relationship between the optical spectra and electronic states. We employ a ferromagnetically ordered state to effectively capture the localized character of the Re 5$d$ electrons. The calculated dielectric function and absorption coefficient qualitatively reproduce the experimentally observed peak structures. An orbital-resolved analysis indicates that the characteristic optical transitions associated with the pleochroism predominantly involve Re-$d$-dominated electronic states, highlighting the key role of the Re $d$ electrons in the pleochroic optical response of Ca$_3$ReO$_5$Cl$_2$.