High-Pressure Structural Evolution of Disordered Polymeric CS2

Year: 2021

Authors: Yan J., Toth O., Xu W., Liu X., Gregoryanz E., Dalladay-Simpson P., Qi Z., Xie S., Gorelli F., Martonak R., Santoro M.

Autors Affiliation: Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China; University of Science and Technology of China, Hefei, 230026, China; Center for High Pressure Science and Technology Advanced Research, 1690 Cailun Road, Shanghai, 201203, China: Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University in Bratislava, Mlynskb Dolina F2, Bratislava, 842 48, Slovakia; School of Physics and Astronomy, Centre for Science at Extreme Conditions, University of Edinburgh, Edinburgh, EH9 3JZ, United Kingdom; National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, China; Istituto Nazionale di Ottica (CNR-INO), European Laboratory for Non Linear Spectroscopy (LENS), via N. Carrara 1, Sesto Fiorentino, 50019, Italy

Abstract: Carbon disulfide is an archetypal double-bonded molecule belonging to the class of group IV-group VI, AB(2) compounds. It is widely believed that, upon compression to several GPa at room temperature and above, 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 this polymer is different. Solid molecular CS2 polymerizes at similar to 10-11 GPa. The polymer is disordered and consists of a mixture of 3-fold (C3) and 4-fold (C4) coordinated carbon atoms with some C=C double bonds. The C4/C3 ratio continuously increases upon further compression to 40 GPa. Upon decompression, structural changes are partially reverted, while the sample also undergoes partial disproportionation. Our work uncovers the nontrivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.

Journal/Review: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS

Volume: 12 (30)      Pages from: 7229  to: 7235

More Information: O.T. and R.M. were supported by the VEGA project (No. 1/0640/20) and the Slovak Research and Development Agency, under Contract No. APVV-19-0371. Calculations were performed at the Computing Centre of the Slovak Academy of Sciences using the supercomputing infrastructure acquired in ITMS Projects No. 26230120002 and No. 26210120002 (Slovak Infrastructure for High-Performance Computing) supported by the Research and Development Operational Programme funded by the ERDF. This work was supported by Youth Innovation Promotion Association of CAS (No. 2021446), National Natural Science Foundation of China (Grant Nos. 11874361, 51672279, 51727806 and 11774354), Innovation Grant of CAS (No. CXJJ-19-B08), Science Challenge Project (No. TZ2016001), CASHIPS Director´s Fund (Grant No. YZJJ201705) and CAS President´s International Fellowship Initiative Fund (No. 2019VMA0027).
KeyWords: carbon-dioxide; crystal-structure; cristobalite; coordination
DOI: 10.1021/acs.jpclett.1c01762

Citations: 5
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