New insights of QTAIM and stress tensor to finding non-competitive/competitive torquoselectivity of cyclobutene

摘要

This study aims to investigate the phenomenon of torquoselectivity through three thermal cyclobutene ring-opening reactions (N1-N3). This research focuses on the nature of the chemical bond, electronic reorganization, predicting non-competitive or competitive reactions, and torquoselectivity preference within Quantum Theory of Atoms in Molecules (QTAIM) and stress tensor frameworks. Various theoretical analyses for these reactions, such as metallicity xi(r(b)), ellipticity epsilon, total local energy density H(r(b)), stress tensor polarizability DOUBLE-STRUCK CAPITAL P-s, stress tensor eigenvalue xi(3s), and bond-path length, display differently for non-competitive and competitive reactions as well as for the conrotatory preferences either it is the transition state outward conrotatory (TSout) or transition state inward conrotatory (TSin) directions by presenting degeneracy or non-degeneracy in their results. The ellipticity profile provides the motion of the bond critical point locations due to the different substituents of cyclobutene. In agreement with experimental results, examinations demonstrated that N1 is a competitive reaction and N2-N3 are non-competitive reactions with TSout and TSin preference directions, respectively. The concordant results of QTAIM and stress tensor scalar and vectors with experimental results provide a better understanding of reaction mechanisms. Published under an exclusive license by AIP Publishing