Metavalent multicenter bonding in pnictogens and chalcogens: nature and mechanism of formation

• DOI: 10.26434/chemrxiv-2023-pv66p-v2
• Publication Date: 2023-12-01T09:42:55Z
• Authors: Hussien H. Osman; Alberto Otero-de-...; Placida Rodríguez...; Alfonso Muñoz; Francisco Javier ...
• Keywords: Chalcogen; Hypervalent molecule; Electron counting

Due to the exceptional property portfolio and technological applications of phase change materials, mostly chalcogens related IV-VI V2-VI3 families, which are in turn pnictogens (group V or 15) VI 16), nature unconventional chemical bonding these materials has been debated for almost 70 years. This bond, quoted literature as resonant, hypervalent, electron-rich multicenter, three-center-four-electron (3c-4e), metavalent, is believed be responsible properties materials. In last decade, two models, metavalent multicenter have competed explain this we here renamed bond (MMB) sake clarity. comprehensive work, address MMB propose that an electron-deficient (EDMB), threecenter-two-electron (3c-2e) bond. For purpose, explore pressure-induced mechanism formation some simplest possible systems, (As, Sb, Bi) (Se, Te, Po), with density-functional theory calculations. way, find polonium only element among crystalline α β structures already exhibiting MMBs at RP. We (chalcogens) comprised three (two) stages, similar EDMB B2H6, Zintl phases, intermetallics, cluster compounds, atomic/polymeric nitrogen hydrogen high pressures. On other hand, completely different from 3c-4e molecules. Finally, geometries EDMBs can found solids along one, two, dimensions comment on validity doublet/octet rules hypercoordinated units EDMBs.