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

Date

2021-11-24

Advisors

Journal Title

Journal ISSN

ISSN

0021-9606

Volume Title

Publisher

American Institute of Physics (AIP) Publishing

Type

Article

Peer reviewed

Yes

Abstract

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 ξ(rb), ellipticity ε, total local energy density H(rb), stress tensor polarizability Pσ , stress tensor eigenvalue λ3σ , 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

Description

The file attached to this record is the Publisher's final version.

Keywords

bond critical point, QTAIM, ring-opening reaction

Citation

Momen, R., Azizi, A., Morales-Bayuelo, A., Pazhoohesh, M., Ji, X. (2021) New insights of QTAIM and stress tensor to finding non-competitive/competitive torquoselectivity of cyclobutene. The Journal of Chemical Physics, 155, 204305.

Rights

Research Institute

Institute of Energy and Sustainable Development (IESD)