- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Research

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Letter
  • Open Access

Dynamical Jahn-Teller effects on the generation of electronic ring currents by circularly polarized light

Krishna R. Nandipati1,* and Oriol Vendrell1,2,†

  • 1Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg, Germany
  • 2Centre for Advanced Materials, Universität Heidelberg, Im Neuenheimer Feld 205, 69120 Heidelberg, Germany

  • *krishna.nandipati@pci.uni-heidelberg.de
  • †oriol.vendrell@uni-heidelberg.de
PDF

Phys. Rev. Research 3, L042003 – Published 8 October, 2021

DOI: https://doi.org/10.1103/PhysRevResearch.3.L042003

Abstract

The generation of electronic ring currents in ring-shaped molecules by photoexcitation with circularly polarized laser light is considered in the presence of vibronic coupling effects. (E×e) Jahn-Teller distortions, unavoidable by symmetry in the (E) subset of electronic states supporting the ring current, mix the clockwise and anticlockwise circulation directions of the electrons and can suppress the maximum achievable current by at least one order of magnitude, already for moderate vibronic coupling strengths, as compared to the Born-Oppenheimer limit of fixed atomic positions. The circulation direction of the electrons is found to depend on the spectral region of the (E×e) Hamiltonian. This fact results in the surprising effect that the same polarization direction of the laser pulse can trigger either clockwise or anticlockwise electronic dynamics depending on the wavelength of the photons. These findings are illustrated in a model of the triazine molecule.

View figure in article

Physics Subject Headings (PhySH)

Corrections

12 November, 2021

Correction: A minor error in the caption to Figure 2 has been fixed. The acronym LCPs has been changed to RCPs.

Article Text

Supplemental Material

References (40)

  1. B. Kudisch, M. Maiuri, L. Moretti, M. B. Oviedo, L. Wang, D. G. Oblinsky, R. K. Prudhomme, B. M. Wong, S. A. McGill, and G. D. Scholes, Ring currents modulate optoelectronic properties of aromatic chromophores at 25 T, Proc. Natl. Acad. Sci. USA 117, 11289 (2020).
  2. K. Kaiser, L. M. Scriven, F. Schulz, P. Gawel, L. Gross, and H. L. Anderson, An sp-hybridized molecular carbon allotrope, cyclo[18]carbon, Science 365, 1299 (2019).
  3. I. Barth, J. Manz, Y. Shigeta, and K. Yagi, Unidirectional electronic ring current driven by a few cycle circularly polarized laser pulse: Quantum model simulations for Mg-porphyrin, J. Am. Chem. Soc. 128, 7043 (2006).
  4. J. E. Anthony, Functionalized acenes and heteroacenes for organic electronics, Chem. Rev. 106, 5028 (2006).
  5. E. Räsänen, A. Castro, J. Werschnik, A. Rubio, and E. K. U. Gross, Optimal Control of Quantum Rings by Terahertz Laser Pulses, Phys. Rev. Lett. 98, 157404 (2007).
  6. M. Galperin, M. A. Ratner, A. Nitzan, and A. Troisi, Nuclear coupling and polarization in molecular transport junctions: Beyond tunneling to function, Science 319, 1056 (2008).
  7. D. Rai, O. Hod, and A. Nitzan, Circular currents in molecular wires, J. Phys. Chem. C 114, 20583 (2010).
  8. K. K. Saha, B. K. Nikolić, V. Meunier, W. Lu, and J. Bernholc, Quantum-Interference-Controlled Three-Terminal Molecular Transistors Based on a Single Ring-Shaped Molecule Connected to Graphene Nanoribbon Electrodes, Phys. Rev. Lett. 105, 236803 (2010).
  9. C. Ramírez and L. Medina-Amayo, Scattering matrix of arbitrary tight-binding Hamiltonians, Ann. Phys. 378, 303 (2017).
  10. M. D. Peeks, T. D. W. Claridge, and H. L. Anderson, Aromatic and antiaromatic ring currents in a molecular nanoring, Nature (London) 541, 200 (2017).
  11. I. Barth and J. Manz, Quantum switching of magnetic fields by circularly polarized re-optimized π laser pulses: From one-electron atomic ions to molecules, in Progress in Ultrafast Intense Laser Science VI (Springer, Berlin, 2010), pp. 21–44.
  12. K.-J. Yuan, C.-C. Shu, D. Dong, and A. D. Bandrauk, Attosecond dynamics of molecular electronic ring currents, J. Phys. Chem. Lett. 8, 2229 (2017).
  13. D. Jia, J. Manz, B. Paulus, V. Pohl, J. C. Tremblay, and Y. Yang, Quantum control of electronic fluxes during adiabatic attosecond charge migration in degenerate superposition states of benzene, Chem. Phys. 482, 146 (2017).
  14. M. Kanno, H. Kono, and Y. Fujimura, Laser-control of ultrafast π-electron ring currents in aromatic molecules: Roles of molecular symmetry and light polarization, Appl. Sci. 8, 2347 (2018).
  15. C. M. Liu, J. Manz, K. Ohmori, C. Sommer, N. Takei, J. C. Tremblay, and Y. Zhang, Attosecond Control of Restoration of Electronic Structure Symmetry, Phys. Rev. Lett. 121, 173201 (2018).
  16. H. A. Jahn and E. Teller, Stability of polyatomic molecules in degenerate electronic states - I—orbital degeneracy, Proc. R. Soc. London, Ser. A 161, 220 (1937).
  17. H. C. Longuet-Higgins, U. Öpik, M. H. L. Pryce, and R. A. Sack, Studies of the Jahn–Teller effect. II. The dynamical problem, Proc. R. Soc. London, Ser. A 244, 1 (1958).
  18. R. Englman, The Jahn–Teller Effect in Molecules and Crystals (Wiley, New York, 1972).
  19. H. Köppel, W. Domcke, and L. Cederbaum, Multimode molecular dynamics beyond the Born–Oppenheimer approximation, Adv. Chem. Phys. 57, 59 (1984).
  20. K. R. Nandipati and O. Vendrell, On the generation of electronic ring currents under vibronic coupling effects, J. Chem. Phys. 153, 224308 (2020).
  21. M. Kanno, H. Kono, Y. Fujimura, and S. H. Lin, Nonadiabatic Response Model of Laser-Induced Ultrafast π-Electron Rotations in Chiral Aromatic Molecules, Phys. Rev. Lett. 104, 108302 (2010).
  22. W. Domcke, D. Yarkony, and H. Köppel, Conical Intersections: Electronic Structure, Dynamics & Spectroscopy, Vol. 15 (World Scientific, Singapore, 2004).
  23. W. Domcke, D. R. Yarkony, and H. Köppel, Conical Intersections: Theory, Computation and Experiment, Vol. 17 (World Scientific, Singapore, 2011).
  24. C. Jungen, The Renner-Teller effect revisited 40 years later, J. Mol. Spectrosc. 363, 111172 (2019).
  25. Z. Li, M. E.-A. Madjet, O. Vendrell, and R. Santra, Correlated Dynamics of the Motion of Proton-Hole Wave Packets in a Photoionized Water Cluster, Phys. Rev. Lett. 110, 038302 (2013).
  26. C. Arnold, O. Vendrell, and R. Santra, Electronic decoherence following photoionization: Full quantum-dynamical treatment of the influence of nuclear motion, Phys. Rev. A 95, 033425 (2017).
  27. V. Despré, A. Marciniak, V. Loriot, M. C. E. Galbraith, A. Rouzée, M. J. J. Vrakking, F. Lépine, and A. I. Kuleff, Attosecond hole migration in benzene molecules surviving nuclear motion, J. Phys. Chem. Lett. 6, 426 (2015).
  28. W. Moffitt and A. Liehr, Configurational instability of degenerate electronic states, Phys. Rev. 106, 1195 (1957).
  29. M. D. Sturge, The Jahn–Teller effect in solids, Solid State Phys. 20, 91 (1968).
  30. R. L. Whetten, K. S. Haber, and E. R. Grant, The dynamic Jahn–Teller effect in sym-triazine: Nonadiabatic wave functions and hindered fluxionality, J. Chem. Phys. 84, 1270 (1986).
  31. I. Barth and J. Manz, Periodic electron circulation induced by circularly polarized laser pulses: Quantum model simulations for Mg porphyrin, Angew. Chem., Int. Ed. 45, 2962 (2006).
  32. A. Messiah, Quantum Mechanics (Dover, New York, 1999).
  33. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevResearch.3.L042003 for the derivation of the ring current expression for the vibronically coupled E states, coupling matrix elements of the (E×e) JT Hamiltonian, and the eigenstates' ring current under quadratic (E×e) JT coupling.
  34. M. Born and K. Huang, Dynamical Theory of Crystal Lattices (Clarendon, Oxford, UK, 1954).
  35. I. Barth, J. Manz, and L. Serrano-Andrés, Quantum simulations of toroidal electric ring currents and magnetic fields in linear molecules induced by circularly polarized laser pulses, Chem. Phys. 347, 263 (2008).
  36. S. Eckart, M. Kunitski, M. Richter, A. Hartung, J. Rist, F. Trinter, K. Fehre, N. Schlott, K. Henrichs, L. P. H. Schmidt et al., Ultrafast preparation and detection of ring currents in single atoms, Nat. Phys. 14, 701 (2018).
  37. I. B. Bersuker, The Jahn-Teller effect (Cambridge University Press, Cambridge, UK, 2006).
  38. L. Pauling and E. B. Wilson, Jr., Introduction to Quantum Mechanics: With Applications to Chemistry (McGraw-Hill, New York, 1935).
  39. G. Gallup, Matrix elements and eigenfunctions of multidimensional oscillators by operational methods: Part I. Two dimensional isotropic harmonic oscillator, J. Mol. Spectrosc. 3, 148 (1959).
  40. G. Worth, A model Hamiltonian to simulate the complex photochemistry of benzene, J. Photochem. Photobiol., A 190, 190 (2007).

Outline

Information

Phys. Rev. Research 3, L042003– Published 8 October, 2021
  • Received 26 May 2021
  • Accepted 9 September 2021
  • Corrected 12 November 2021
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation