TY - JOUR

T1 - Visualizing and comparing quantum interference in the π -system and σ -system of organic molecules

AU - Cao, Ning

AU - Bro-Jørgensen, William

AU - Zheng, Xiaohong

AU - Solomon, Gemma C.

N1 - 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).

PY - 2023

Y1 - 2023

N2 - 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.

AB - 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.

U2 - 10.1063/5.0141577

DO - 10.1063/5.0141577

M3 - Journal article

C2 - 37003722

AN - SCOPUS:85150891717

VL - 158

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 12

M1 - 124305

ER -