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The results of global\u2010minimum structural searches indicate the N\n 6<\/jats:sub>\n prefers a trimer\u2010like\n C<\/jats:italic>\n \n 3<\/jats:italic>\n <\/jats:sub>\n geometry, while P\n 6<\/jats:sub>\n \/As\n 6<\/jats:sub>\n tends to form the bag\u2010like\n C<\/jats:italic>\n \n 2v<\/jats:italic>\n <\/jats:sub>\n structure, and Sb\n 6<\/jats:sub>\n \/Bi\n 6<\/jats:sub>\n prefers the triangular prism\n D<\/jats:italic>\n \n 3h<\/jats:italic>\n <\/jats:sub>\n structure energetically instead. Simulated infrared spectra reveal the trimer\u2010like N\n 6<\/jats:sub>\n exhibiting an isolated high\u2010frequency triple\u2010bond stretching band far separated from the low\u2010frequency single\u2010bond skeletal vibration regimes of heavier pnictogen hexamers. Canonical molecular orbital analyses reveal a non\u2010monotonic periodic evolution of HOMO\u2013LUMO electronic band gaps, with N\n 6<\/jats:sub>\n , Sb\n 6<\/jats:sub>\n and Bi\n 6<\/jats:sub>\n possessing substantially wider frontier orbital energy separation relative to narrow\u2010gap bag\u2010like P\n 6<\/jats:sub>\n and As\n 6<\/jats:sub>\n species. Multi\u2010modal wavefunction analytical tools including AdNDP, QTAIM, ELF, IRI and RDG\/NCI resolve continuous periodic evolution of covalent bonding motifs from discrete diatomic triple bonds in N\n 6<\/jats:sub>\n , mixed\n \u03c3<\/jats:italic>\n and\n \u03c0<\/jats:italic>\n bonding in P\n 6<\/jats:sub>\n and As\n 6<\/jats:sub>\n , to pure localized\n \u03c3<\/jats:italic>\n single\u2010bonded frameworks devoid of\n \u03c0<\/jats:italic>\n orbital contributions in Sb\n 6<\/jats:sub>\n and Bi\n 6<\/jats:sub>\n . Quantified dissociation energy values for two representative uni\u2010molecular fragmentation pathways demonstrate monotonically increasing resistance to full decomposition from N\n 6<\/jats:sub>\n to Bi\n 6<\/jats:sub>\n . Additional SOC\u2010CASSCF energy level calculations further quantify the progressive intensification of spin\u2010orbit coupling relativistic effects down group 15, which exert negligible electronic perturbation on N\n 6<\/jats:sub>\n and P\n 6<\/jats:sub>\n , moderate orbital splitting for As\n 6<\/jats:sub>\n , and decisive rearrangement of frontier orbital manifolds for Sb\n 6<\/jats:sub>\n and Bi\n 6<\/jats:sub>\n that dictates geometric stability preferences of heavy hexamer prism. This work systematically reveals the periodic evolution law of group VA X\n 6<\/jats:sub>\n molecules, providing key theoretical insights for the design and synthesis of novel pnictogen clusters.\n <\/jats:p>","DOI":"10.1002\/jcc.70479","type":"journal-article","created":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T10:42:21Z","timestamp":1786444941000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Structure, Stability, Spectroscopy and Chemical Bonding Analyses on the Novel X\n 6<\/sub>\n (X\u2009=\u2009N, P, As, Sb, Bi) Molecules"],"prefix":"10.1002","volume":"47","author":[{"given":"Yu","family":"Cheng","sequence":"first","affiliation":[{"name":"School of Rare Earths University of Science and Technology of China Hefei China"},{"name":"Fundamental Science Center of Rare Earths Ganjiang Innovation Academy, Chinese Academy of Sciences Ganzhou Jiangxi 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