An unusual set of anomalous functional properties of rocksalt crystals of Group IV chalcogenides were recently linked to a kind of bonding termed as metavalent bonding (MVB) which involves violation of the 8‐N rule. Precise mechanisms of MVB and the relevance of lone pair of Group IV cations are still debated. With restrictions of low dimensionality on the possible atomic coordination, 2D materials provide a rich platform for exploration of MVB. Here, we present first‐principles theoretical analysis of the nature of bonding in five distinct 2D lattices of Group IV chalcogenides MX (M: Sn, Pb, Ge and X: S, Se, Te), in which the natural out‐of‐plane expression of the lone pair versus in‐plane bonding can be systematically explored. While their honeycomb lattices respecting the 8‐N rule are shown to exhibit covalent bonding, their square and orthorhombic structures exhibit MVB only in‐plane, with cationic lone pair activating the out‐of‐plane structural puckering that controls their relative stability. Anomalies in Born‐effective charges, dielectric constants, Grüneisen parameters occur only in their in‐plane behaviour, confirming MVB is confined strictly to 2D and originates from p‐p orbital interactions. Our work opens up directions for chemical design of MVB based 2D materials and their heterostructures.
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