Antiferromagnetic spin-frustrated layers of corner-sharing Cu4 tetrahedra on the kagome lattice in volcanic minerals Cu5O2(VO4)2(CuCl), NaCu5O2(SeO3)2Cl3, and K2Cu5Cl8(OH)4 2H2O

TL;DR

This study investigates the potential for quantum spin liquids in three volcanic minerals by analyzing their crystal structures, magnetic interactions, and geometric frustrations, revealing complex AFM spin-frustrated layers on the kagome lattice.

Contribution

It provides a detailed structural and magnetic analysis of three minerals, highlighting the presence of antiferromagnetic spin frustration on the kagome lattice and the effects of structural variations.

Findings

Averievite and ilinskite have AFM spin-frustrated layers of corner-sharing Cu4 tetrahedra.

Structural differences lead to different magnetic interactions and potential for spin fluctuations.

Removing oxygen ions transforms the magnetic structure into a complex openwork net.

Abstract

The objective of the present work was to analyze the possibility of realization of quantum spin liquid in three volcanic minerals - averievite (Cu5O2(VO4)2(CuCl)), ilinskite (NaCu5O2(SeO3)2Cl3), and avdononite (K2Cu5Cl8(OH)4 2H2O - from the crystal chemistry point of view. Based on the structural data, the sign and strength of magnetic interactions have been calculated and the geometric frustrations serving as the main reason of the existence of spin liquids have been investigated. According to our calculations, the magnetic structures of averievite and ilinskite are composed of antiferromagnetic (AFM) spin-frustrated layers of corner-sharing Cu4 tetrahedra on the kagome lattice. However, the direction of nonshared corners of tetrahedra is different in them. The oxygen ions centering the OCu4 tetrahedra in averievite and ilinskite provide the main contribution to the formation of AFM interactions along the tetrahedra edges. The local electric polarization in averievite and the possibility of spin configuration fluctuations due to vibrations of tetrahedra-centering oxygen ions have been discussed. The existence of structural phase transitions accompanied with magnetic transitions was assumed in ilinskite because of the effect of a lone electron pair by Se4+ ions. As was demonstrated through comparison of averievite and avdoninite, at the removal of centering oxygen ions from tetrahedra, the magnetic structure of the pyrochlore layer present in averievite transformed into an openwork curled net with large cells woven from corner-sharing open AFM spin-frustrated tetrahedra ('butterflies'} in avdoninite.