High-Pressure Structural Evolution of Disordered Polymeric CS$_2$

TL;DR

This study reveals that under high pressure, CS$_2$ transforms into a disordered polymeric structure with increasing carbon coordination, challenging previous assumptions of a simple chain polymer formation.

Contribution

The paper demonstrates that the high-pressure structure of CS$_2$ is a disordered polymer, not the expected chain polymer, based on combined spectroscopy, diffraction, and ab initio simulations.

Findings

CS$_2$ undergoes a structural transformation at 10-11 GPa.

The polymer has 3-fold and 4-fold coordinated carbons.

Partial recovery and disproportionation occur upon decompression.

Abstract

Carbon disulfide, CS$_2$, is an archetypal double-bonded molecular system belonging to the rich class of group IV-group VI, AB$_2$ compounds. It is widely and since long time believed that upon compression at several GPa a polymeric chain of type (-(C=S)-S-)$_n$ named Bridgman's black polymer will form. By combining optical spectroscopy and synchrotron X-ray diffraction data with ab initio simulations, we demonstrate that the structure of the Bridgman's black polymer is remarkably different. Solid molecular CS$_2$ undergoes a pressure-induced structural transformation at around 10-11 GPa, developing a disordered polymeric system. The polymer consists of 3-fold and 4-fold coordinated carbon atoms with an average carbon coordination continuously increasing upon further compression to 40 GPa. Polymerization also gives rise to some C=C double bonds. Upon decompression, the structural changes are partially reverted, a very small amount of molecular CS$_2$ is recovered, while the sample undergoes partial chemical disproportionation. Our work uncovers the non-trivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.