Structural phase transformation of quantum spin liquid herbertsmithite via pressure induced enhancement of the cooperative Jahn–Teller effect and antisite disorder

Abstract

Herbertsmithite, Cu₃Zn(OH)₆Cl₂, serves as one of the most promising candidates for quantum spin liquids with a perfect quantum kagome Heisenberg antiferromagnetic system. It can comprise an ideal model system for studying the compression response of the unique structure as well as exotic properties of kagome quantum spin liquid materials, which is of fundamental importance from both scientific and technological viewpoints. In this work, the structural evolution of herbertsmithite was investigated via in situ X-ray diffraction and Raman scattering techniques up to 30 GPa. The trigonal herbertsmithite structure transformed into a monoclinic clinoatacamite-like structure at 12.6 GPa. High pressure seems to act in a reverse way as Zn-doping for herbertsmithite, with the distortion degree of the system changing continuously. The occurrence of the displacive and reversible phase transition between the polymorphs is a consequence of the interplay between the external pressure and cooperative Jahn–Teller (JT) effect, aided by the presence of antisite mutual substitution of magnetic Cu²⁺ ions and nonmagnetic Zn²⁺ ions between the kagome layer and interlayer sites.