1. High-Pressure Structural Evolution of Disordered Polymeric CS$_2$
- Author
-
Yan, Jinwey, Tóth, Ondrej, Xu, Wan, Liu, Xiao-Di, Gregoryanz, Eugene, Dalladay-Simpson, Philip, Qi, Zeming, Xie, Shiyu, Gorelli, Federico, Martoňák, Roman, and Santoro, Mario
- Subjects
Condensed Matter - Other Condensed Matter ,Condensed Matter - Disordered Systems and Neural Networks - 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., Comment: 8 pages, 5 figures, supplementary materials more...
- Published
- 2021