High-pressure and high-temperature modulation of one-dimensional infinite chain in SeO2

• Published in: Applied physics letters Vol. 124; no. 14
• Main Authors: Lu, Wencheng, Liu, Siyu, Cai, Jinqun, Ning, Ping, Ma, Chuanheng, Liu, Guangtao, Wang, Hongbo, Guo, Qing, Zhou, Mi, Wang, Yanchao, Ma, Yanming
• Format: Journal Article
• Language: English
• Published: Melville American Institute of Physics 01.04.2024
• Subjects: Algorithms; Compressibility; Diamond anvil cells; First principles; High pressure; High temperature; Laser beam heating; Modulation; Phase diagrams; Pyramids; Selenium dioxide; Swarm intelligence; Synchrotron radiation
• ISSN: 0003-6951; 1077-3118
• DOI: 10.1063/5.0196686

The structural evolution of lone-pair compounds under high-pressure and high-temperature conditions has been a subject of fundamental interest in revealing modulated polymorphs. As one of the archetypal lone-pair compounds, selenium dioxide (SeO2) has attracted much attention due to the pressure modulation of its one-dimensional infinite W-shaped chain arrangement. Here, through swarm intelligence algorithm in conjunction with the first-principles simulation, we propose the existence of an orthorhombic Pnma-SeO2 structure, characterized by V-shaped chains interconnected via vertex-sharing SeO3 pyramids. These V-shaped chains demonstrate reduced compressibility along their chain direction compared to the W-shaped chains. Calculations indicate that Pnma-SeO2 is a semiconductor with a large indirect bandgap of 2.39 eV. Remarkably, we synthesized the predicted Pnma-SeO2 in a laser-heated diamond anvil cell at a pressure of 48.5 or 87 GPa as identified by in situ synchrotron x-ray diffraction data. Our findings lead to a significant extension of the phase diagram and transition path of SeO2 and provide key insights into understanding the pressure modulation in lone-pair compounds.