Revisiting the bonding evolution theory: a fresh perspective on the ammonia pyramidal inversion and bond dissociations in ethane and borazane.

Abstract

This work offers a comprehensive and fresh perspective on the bonding evolution theory (BET) framework, originally proposed by Silvi and collaborators [X. Krokidis, S. Noury and B. Silvi, Characterization of elementary chemical processes by catastrophe theory, J. Phys. Chem. A, 1997, 101, 7277-7282]. By underscoring Thom's foundational work, we identify the parametric function characterizing bonding events along a reaction pathway through a three-step sequence to establish such association rigorously, namely: (a) computing the determinant of the Hessian matrix at all potentially degenerate critical points, (b) computing the relative distance between these points, and (c) assigning the unfolding based on these computations and considering the maximum number of critical points for each unfolding. In-depth examination of the ammonia inversion and the dissociation of ethane and ammonia borane molecules yields a striking discovery: no elliptic umbilic flag is detected along the reactive coordinate for any of the systems, contradicting previous reports. Our findings indicate that the core mechanisms of these chemical reactions can be understood using only two folds, the simplest polynomial of Thom's theory, leading to considerable simplification. In contrast to previous reports, no signatures of the elliptic umbilic unfolding were detected in any of the systems examined. This finding dramatically simplifies the topological rationalization of electron rearrangements within the BET framework, opening new approaches for investigating complex reactions.