Visualizing and comparing quantum interference in the π -system and σ -system of organic molecules
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Quantum interference effects in conjugated molecules have been well-explored, with benzene frequently invoked as a pedagogical example. These interference effects have been understood through a quantum interference map in which the electronic transmission is separated into interfering and non-interfering terms, with a focus on the π-orbitals for conjugated molecules. Recently, saturated molecules have also been reported to exhibit destructive quantum interference effects; however, the very different σ-orbital character in these molecules means that it is not clear how orbital contributions manifest. Herein, we demonstrate that the quantum interference effects in conjugated molecules are quite different from those observed in saturated molecules, as demonstrated by the quantum interference map. While destructive interference at the Fermi energy in the π-system of benzene arises from interference terms between paired occupied and virtual orbitals, this is not the case at the Fermi energy in saturated systems. Instead, destructive interference is evident when contributions from a larger number of non-paired orbitals cancel, leading to more subtle and varied manifestations of destructive interference in saturated systems.
Original language | English |
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Article number | 124305 |
Journal | Journal of Chemical Physics |
Volume | 158 |
Issue number | 12 |
Number of pages | 9 |
ISSN | 0021-9606 |
DOIs | |
Publication status | Published - 2023 |
Bibliographical note
Funding Information:
We gratefully acknowledge financial support from the National Natural Science Foundation of China under Grant No. 11974355 (X.Z.) and the China Scholarship Council (N.C.). This project received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation program (Grant Agreement No. 865870).
Publisher Copyright:
© 2023 Author(s).
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