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

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 genera...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2021-11, Vol.17 (11), p.6901-6909
Main Authors: Hasebe, Masatoshi, Tsutsumi, Takuro, Taketsugu, Tetsuya, Tsuneda, Takao
Format: Article
Language:English
Subjects:
Chemical reactions
Electron transfer
Energy methods
Energy theory
Orbitals
Potential energy
Quantum Electronic Structure
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Summary: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.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.1c00693