One-to-One Correspondence between Reaction Pathways and Reactive Orbitals

Masatoshi Hasebe; Takuro Tsutsumi; Tetsuya Taketsugu; Takao Tsuneda

doi:10.1021/acs.jctc.1c00693

One-to-One Correspondence between Reaction Pathways and Reactive Orbitals

J Chem Theory Comput. 2021 Nov 9;17(11):6901-6909. doi: 10.1021/acs.jctc.1c00693. Epub 2021 Oct 25.

Authors

Masatoshi Hasebe¹, Takuro Tsutsumi², Tetsuya Taketsugu^{2

3}, Takao Tsuneda^{2

4}

Affiliations

¹ Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan.
² Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
³ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan.
⁴ Graduate School of Science Technology and Innovation, Kobe University, Nada-ku, Kobe, Hyogo 657-8501, Japan.

PMID: 34694803
DOI: 10.1021/acs.jctc.1c00693

Abstract

The one-to-one correspondence between reaction pathways in the potential energy theory and reactive orbitals in the electronic theory for reactions is presented. In this study, the reactive orbital energy method is applied to the intrinsic reaction coordinates of the global reaction route map generated by an automated reaction path search method. The reactive orbital energy method specifies the pairs of occupied and unoccupied reactive orbitals driving chemical reactions and determines whether the reactions are electron transfer-driven or dynamics-driven. Surprisingly, it is found that the reactive orbital pairs are determined one by one for the electron transfer-driven reaction pathways from an identical molecule. The reactive orbital energy method is also found to provide the sophisticated interpretations of reactions for the electronic motions. This one-to-one correspondence is expected to trigger the unification of the potential energy theory and the electronic theory for reactions that have been independently developed.