Ligand-metal covalency effects in resonance enhanced x-ray Bragg diffraction

TL;DR

This paper investigates how ligand-metal covalency influences resonance-enhanced x-ray Bragg diffraction, focusing on chlorine compounds with unique electronic and structural properties, using symmetry-based calculations and experimental data.

Contribution

It introduces a symmetry-inspired calculation method for analyzing chlorine multipoles in resonance-enhanced x-ray diffraction, applied to various chlorine-metal compounds.

Findings

Chlorine K-edge features relate to metal-ligand bonds.

Bragg diffraction patterns are simpler in certain rhombohedral compounds.

Resonant x-ray diffraction confirms structural chirality in CsCuCl3.

Abstract

Chlorine covalently bonded to an open shell metal is present in many materials with desirable or intriguing physical properties. Materials include highly luminescent nontoxic alternatives to lead halide perovskites for optoelectronic applications K2CuCl3 and Rb2CuCl3, enantiomorphic CsCuCl3 that presents magneto-chiral dichroism at a low temperature, and cubic K2RuCl6 that possesses a singlet ground state generated by antiparallel spin and orbital angular momenta. Structural chirality of CsCuCl3 has been confirmed by resonant x-ray Bragg diffraction. We explore likely benefits of the technique at the chlorine K-edge using a symmetry inspired method of calculation applied to chlorine multipoles. Already, a low energy feature in corresponding x-ray absorption spectra of many compounds has been related to the chlorine-metal bond. Bragg diffraction from chlorine in cubic K2RuCl6 is treated in detail. Diffraction patterns for rhombohedral compounds that present space-group forbidden Bragg spots are found to be relatively simple.