The Coherent Rotation of π-Electron in a Small Aromatic Molecule
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Abstract
Coherent rotation is a typical form of charge migration in aromatic molecules, in which π-electron rotates along the ring loop of molecule. Within a quantum-mechanical framework, the π-electron rotation can be characterized by the expectation values of observable operators, including angular momentum and current density. These quantities can be evaluated using analytical expressions combined with ab initio quantum-chemical calculations by Gaussian in H. Mineo, et al., (2013); an approach that is applicable to a wide range size of aromatic molecules. In this work, we apply this approach to investigate the coherent rotation of π-electron in a simple aromatic, s-triazine (C3H3N3), which belongs to the D3h symmetry group. Ring currents are identified not only along rings consisting of carbon-carbon atoms, or nitrogen-nitrogen atoms, but also along rings involving the nearest neighbor carbon-nitrogen pairs. The magnitude of bond current is determined from the total flux crossing a plane located at the midpoint of each bond connecting two atoms. To visualize the spatial distribution of the current density, current-density maps are plotted on a plane parallel to the molecular plane at a distance of z=1.0 Å.
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Atkins, P., & Friedman, R. (2005). Molecular orbital theory of polyatomic molecules. In Molecular quantum mechanics (4th ed., p. 266). Oxford University Press.
Barth, I., Manz, J., Shigeta, Y., & Yagi, K. (2006). Unidirectional electronic ring current driven by a few-cycle circularly polarized laser pulse: Quantum model simulations for Mg-porphyrin. Journal of the American Chemical Society, 128, 7043–7049. https://doi.org/10.1021/ja057197l
Frisch, M. J., Trucks, G. W., Schlegel, H. B., & co-authors. (2016). Gaussian 09 [Computer software]. Gaussian, Inc. https://www.gaussian.com/g09citation/
Flowler, P. W., and Steiner, E. (1997). Ring Currents and Aromaticity of Monocyclic π-Electron Systems C6H6, B3N3H6, B3O3H3, C3N3H3, C5H5-,C7H7+,C3N3F3,C6H3F3, and C6F6. The Journal of Physical Chemistry A, 101, 1409-1413. https://pubs.acs.org/doi/10.1021/jp9637946
Hermann, G., Liu, C., Manz, J., & co-authors. (2016). Multidirectional angular electronic flux during adiabatic attosecond charge migration in excited benzene. The Journal of Physical Chemistry A, 120, 5360–5369. https://doi.org/10.1021/acs.jpca.6b01948
Hsu, L.-Y., Huang, Q.-R., & Jin, B.-Y. (2009). Charge transport through a single molecular wire based on linear multimetal complexes: A non-equilibrium Green’s function approach. The Journal of Physical Chemistry C, 112, 10538–10541. https://doi.org/10.1021/jp801926d
Hsu, L.-Y., & Rabitz, H. (2012). Single-molecule phenyl-acetylene-macrocycle-based optoelectronic switch functioning as a quantum-interference-effect transistor. Physical Review Letters, 109, 186801. https://doi.org/10.1103/physrevlett.109.186801
Jia, D., Manz, J., & Yang, Y. (2019). De- and recoherence of charge migration in ionized iodoacetylene. The Journal of Physical Chemistry Letters, 10, 4273–4277. https://doi.org/10.1021/acs.jpclett.9b01687
Kanno, M., Abe, M., Nakajima, T., Hoki, K., & Fujimura, Y. (2006). Control of π-electron rotation in chiral aromatic molecules by nonhelical laser pulses. Angewandte Chemie International Edition, 45, 7995–7998. https://doi.org/10.1002/anie.200602479
Krause, P., Klamroth, T., & Saalfrank, P. (2005). Time-dependent configuration-interaction calculations of laser-pulse-driven many-electron dynamics: Controlled dipole switching in lithium cyanide. The Journal of Chemical Physics, 123, 074105. https://doi.org/10.1063/1.1999636
Kumar, B. G., & Prakash, K. S. (2021). Nanoelectronics and photonics for next-generation devices. In the Handbook of polymer and ceramic nanotechnology (p. 293). Springer.
Mineo, H., Lin, S.-H., & Fujimura, Y. (2013). Coherent π-electron dynamics of (P)-2,2′-biphenol induced by ultrashort linearly polarized UV pulses: Angular momentum and ring current. The Journal of Chemical Physics, 138, 074304. https://doi.org/10.1063/1.4790595
Mineo, H., & Fujimura, Y. (2017). Quantum control of coherent π-electron ring currents in polycyclic aromatic hydrocarbons. The Journal of Chemical Physics, 147, 224301. https://doi.org/10.1063/1.5004504
Mineo, H., Yamaki, M., Teranishi, Y., & co-authors. (2012). Quantum switching of π-electron rotations in a nonplanar chiral molecule by using linearly polarized UV laser pulses. Journal of the American Chemical Society, 134, 14279–14282. https://doi.org/10.1021/ja3047848
Mohammed, H., Mia, M. F., Wiggins, J., & Desai, S. (2025). Nanomaterials for energy storage systems—A review. Molecules, 30, 883. https://doi.org/10.3390/molecules30040883
Nobusada, K., & Yabana, K. (2007). Photoinduced electric currents in ring-shaped molecules by circularly polarized laser. Physical Review A, 75, 032518. https://doi.org/10.1103/PhysRevA.75.032518
Steiner, E., & Fowler, P. W. (2001). Patterns of ring currents in conjugated molecules: A few-electron model based on orbital contributions. The Journal of Physical Chemistry A, 105, 9553–9562. https://doi.org/10.1021/jp011955m
Steiner, E., Soncini, A., & Fowler, P. W. (2005). Ring currents in the porphyrins: π-shielding, delocalisation pathways and the central cation. Organic & Biomolecular Chemistry, 3, 4053–4059. https://doi.org/10.1039/b511913h
Ulusoy, I. S., & Nest, M. (2011). Correlated electron dynamics: How aromaticity can be controlled. Journal of the American Chemical Society, 133, 20230–20236. https://doi.org/10.1021/ja206193t.