Hidden aspects of the Structural theory of chemistry: MC-QTAIM analysis reveals “alchemical” transformation from a triatomic to a diatomic structure

The Structural theory of chemistry introduces chemical/molecular structure as a combination of relative arrangement and bonding patterns of atoms in a molecule. Nowadays, the structure of atoms in molecules is derived from the topological analysis of the quantum theory of atoms in molecules (QTAIM). In this context, a molecular structure is varied by large geometrical variations and concomitant reorganization of electronic structure that usually take place in chemical reactions or under extreme hydrostatic pressure. In this report, a new mode of structural variation is introduced within the context of the newly proposed multi-component QTAIM (MC-QTAIM) that originates from the mass variation of nuclei. Accordingly, XCN and CNX series of species are introduced where X stands for a quantum particle with a unit of positive charge and a variable mass that is varied in discrete steps between the mass of a proton and a positron. Ab initio non-Born–Oppenheimer (non-BO) calculations are done on both series of species and the resulting non-BO wavefunctions are used for the MC-QTAIM analysis, revealing a triatomic structure for the proton mass and a diatomic structure for the positron mass. In both series of species, a critical mass between that of proton and positron mass is discovered where the transition from triatomic to diatomic structure takes place. This abrupt structural transformation has a topological nature resembling the usual phase transitions in thermodynamics. The discovered mass-induced structural transformation is a hidden aspect of the Structural theory which is revealed only beyond the BO paradigm, when nuclei are treated as quantum waves instead of clamped point charges.