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Photoelectron Circular Dichroism of a Chiral Molecule Induced by Resonant Interatomic Coulombic Decay from an Antenna Atom

Stefan Yoshi Buhmann1,*, Andreas Hans1,†, Janine C. Franz1,2, and Philipp V. Demekhin1,‡

  • *Contact author: stefan.buhmann@uni-kassel.de
  • †Contact author: hans@physik.uni-kassel.de
  • ‡Contact author: demekhin@physik.uni-kassel.de
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Phys. Rev. Lett. 134, 253001 – Published 24 June, 2025

DOI: https://doi.org/10.1103/vrjh-wx5j

Abstract

We show that a nonchiral atom can act as an antenna to induce a photoelectron circular dichroism in a nearby chiral molecule in a three-step process: The donor atom (antenna) is initially resonantly excited by circularly polarized radiation. It then transfers its excess energy to the acceptor molecule by means of resonant interatomic Coulombic decay. The latter finally absorbs the energy and emits an electron that exhibits the aforementioned circular dichroism in its angular distribution. We study the process on the basis of the retarded dipole–dipole interaction and report an asymptotic analytic expression for the distance-dependent chiral asymmetry of the photoelectron as induced by resonant interatomic Coulombic decay for random line-of-sight and acceptor orientations. In the nonretarded limit, the predicted chiral asymmetry is reversed as compared to that of a direct photoelectron circular dichroism of the molecule.

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References (39)

  1. U. Meierhenrich, Amino Acids and the Asymmetry of Life (Springer, Berlin, 2008).
  2. B. Ritchie, Theory of the angular distribution of photoelectrons ejected from optically active molecules and molecular negative ions, Phys. Rev. A 13, 1411 (1976).
  3. N. Böwering, T. Lischke, B. Schmidtke, N. Müller, T. Khalil, and U. Heinzmann, Asymmetry in photoelectron emission from chiral molecules induced by circularly polarized light, Phys. Rev. Lett. 86, 1187 (2001).
  4. G. A. Garcia, L. Nahon, M. Lebech, J.-C. Houver, D. Dowek, and I. Powis, Circular dichroism in the photoelectron angular distribution from randomly oriented enantiomers of camphor, J. Chem. Phys. 119, 8781 (2003).
  5. U. Hergenhahn, E. E. Rennie, O. Kugler, S. Marburger, T. Lischke, I. Powis, and G. Garcia, Photoelectron circular dichroism in core level ionization of randomly oriented pure enantiomers of the chiral molecule camphor, J. Chem. Phys. 120, 4553 (2004).
  6. I. Powis, Photoelectron circular dichroism in chiral molecules, Adv. Chem. Phys. 138, 267 (2008).
  7. L. Nahon, G. A. Garcia, and I. Powis, Valence shell one-photon photoelectron circular dichroism in chiral systems, J. Electron Spectrosc. Relat. Phenom. 204, 322 (2015).
  8. S. Beaulieu, A. Ferré, R. Géneaux, R. Canonge, D. Descamps, B. Fabre, N. Fedorov, F. Légare, S. Petit, T. Ruchon, V. Blanchet, Y. Mairesse, and B. Pons, Universality of photoelectron circular dichroism in the photoionization of chiral molecules, New J. Phys. 18, 102002 (2016).
  9. M. Wollenhaupt, Photoelectron circular dichroism in different ionization regimes, New J. Phys. 18, 121001 (2016).
  10. I. Powis, S. Daly, M. Tia, B. Cunha de Miranda, G. A. Garcia, and L. Nahon, A photoionization investigation of small, homochiral clusters of glycidol using circularly polarized radiation and velocity map electron–ion coincidence imaging, Phys. Chem. Chem. Phys. 16, 467 (2014).
  11. S. Hartweg, G. A. Garcia, D. K. Božanić, and L. Nahon, Condensation effects on electron chiral asymmetries in the photoionization of Serine: From free molecules to nanoparticles, J. Phys. Chem. Lett. 12, 2385 (2021).
  12. E. Rouquet, M. Roy Chowdhury, G. A. Garcia, L. Nahon, J. Dupont, V. Lepère, K. Le Barbu-Debus, and A. Zehnacker, Induced photoelectron circular dichroism onto an achiral chromophore, Nat. Commun. 14, 6290 (2023).
  13. L. S. Cederbaum, J. Zobeley, and F. Tarantelli, Giant intermolecular decay and fragmentation of clusters, Phys. Rev. Lett. 79, 4778 (1997).
  14. T. Jahnke, U. Hergenhahn, B. Winter, R. Dörner, U. Frühling, P. V. Demekhin, K. Gokhberg, L. S. Cederbaum, A. Ehresmann, A. Knie, and A. Dreuw, Interatomic and intermolecular Coulombic decay, Chem. Rev. 120, 11295 (2020).
  15. T. Jahnke, A. Czasch, M. S. Schöffler, S. Schössler, A. Knapp, M. Käsz, J. Titze, C. Wimmer, K. Kreidi, R. E. Grisenti, A. Staudte, O. Jagutzki, U. Hergenhahn, H. Schmidt-Böcking, and R. Dörner, Experimental observation of interatomic Coulombic decay in neon dimers, Phys. Rev. Lett. 93, 163401 (2004).
  16. L. S. Cederbaum, Fragmentation of molecules by virtual photons from remote neighbors, J. Phys. Chem. Lett. 11, 8964 (2020).
  17. S. Barth, S. Joshi, S. Marburger, V. Ulrich, A. Lindblad, G. Öhrwall, O. Björneholm, and U. Hergenhahn, Observation of resonant Interatomic Coulombic decay in Ne clusters, J. Chem. Phys. 122, 241102 (2005).
  18. K. Gokhberg, V. Averbukh, and L. S. Cederbaum, Interatomic decay of inner-valence-excited states in clusters, J. Chem. Phys. 124, 144315 (2006).
  19. A. Knie, A. Hans, M. Förstel, U. Hergenhahn, Ph. Schmidt, Ph. Reiß, Ch. Ozga, B. Kambs, F. Trinter, J. Voigtsberger, D. Metz, T. Jahnke, R. Dörner, A. I. Kuleff, L. S. Cederbaum, Ph. V. Demekhin, and A. Ehresmann, Detecting ultrafast interatomic electronic processes in media by fluorescence, New J. Phys. 16, 102002 (2014).
  20. B. Najjari, A. B. Voitkiv, and C. Müller, Two-center resonant photoionization, Phys. Rev. Lett. 105, 153002 (2010).
  21. F. Trinter et al., Vibrationally resolved decay width of interatomic Coulombic decay in HeNe, Phys. Rev. Lett. 111, 233004 (2013).
  22. A. Hans, Ph. Schmidt, Ch. Ozga, C. Richter, H. Otto, X. Holzapfel, G. Hartmann, A. Ehresmann, U. Hergenhahn, and A. Knie, Efficient fluorescence quenching by distant production of a free electron, J. Phys. Chem. Lett. 10, 1078 (2019).
  23. R. Santra and L. S. Cederbaum, Non-Hermitian electronic theory and applications to clusters, Phys. Rep. 368, 1 (2002).
  24. J. L. Hemmerich, R. Bennett, and S. Y. Buhmann, The influence of retardation and dielectric environments on interatomic Coulombic decay, Nat. Commun. 9, 2934 (2018).
  25. D. P. Craig and T. Thirunamachandran, Chiral discrimination in molecular excitation transfer, J. Chem. Phys. 109, 1259 (1998).
  26. J. C. Franz, S. Y. Buhmann, and A. Salam, Discriminatory resonance energy transfer mediated by a chiral environment, New J. Phys. 26, 053002 (2024).
  27. G. Hartmann, M. Ilchen, Ph. Schmidt, C. Küstner-Wetekam, C. Ozga, F. Scholz, J. Buck, F. Trinter, J. Viefhaus, A. Ehresmann, M. S. Schöffler, A. Knie, and Ph. V. Demekhin, Recovery of high-energy photoelectron circular dichroism through Fano interference, Phys. Rev. Lett. 123, 043202 (2019).
  28. T. Förster, Zwischenmolekulare Energiewanderung und Fluoreszenz, Ann. Phys. (Berlin) 437, 55 (1948).
  29. D. P. Craig and T. Thirunamachandran, Molecular Quantum Electrodynamics (Dover Publishing Inc, New York, 1998).
  30. A. Knie, M. Ilchen, Ph. Schmidt, Ph. Reiß, C. Ozga, B. Kambs, A. Hans, N. Müglich, S. A. Galitskiy, L. Glaser, P. Walter, J. Viefhaus, A. Ehresmann, and Ph. V. Demekhin, Angle-resolved study of resonant Auger decay and fluorescence emission processes after core excitations of the terminal and central nitrogen atoms in N2O, Phys. Rev. A 90, 013416 (2014).
  31. M. Ilchen, G. Hartmann, P. Rupprecht, A. N. Artemyev, R. N. Coffee, Z. Li, H. Ohldag, H. Ogasawara, T. Osipov, D. Ray, Ph. Schmidt, T. J. A. Wolf, A. Ehresmann, S. Moeller, A. Knie, and Ph. V. Demekhin, Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane, Phys. Rev. A 95, 053423 (2017).
  32. N. B. Bejoy, R. K. Singh, N. K. Singh, B. Pananghat, and G. N. Patwari, Dynamics of hydrogen bond breaking induced by outer-valence intermolecular Coulombic decay, J. Phys. Chem. Lett. 14, 5718 (2023).
  33. M. Bohlen, R. Michiels, M. Michelbach, S. Ferchane, M. Walter, A. Eisfeld, and F. Stienkemeier, Excitation dynamics in polyacene molecules on rare-gas clusters, J. Chem. Phys. 156, 034305 (2022).
  34. S. Sen, S. Mandal, S. De, A. Sen, R. Gopal, L. Ben Ltaief, S. Turchini, D. Catone, N. Zema, M. Coreno, R. Richter, M. Mudrich, V. Sharma, and S. R. Krishnan, Electron and ion spectroscopy of camphor doped helium nanodroplets in the extreme UV and soft x-ray regime, J. Phys. B 57, 015201 (2024).
  35. A. Kramida, Yu. Ralchenko, and J. Reader (NIST ASD Team), NIST Atomic Spectra Database (ver. 5.12), Available: https://physics.nist.gov/asd (2024, November 29), National Institute of Standards and Technology, Gaithersburg, MD.
  36. E. E. Rennie, I. Powis, U. Hergenhahn, O. Kugeler, G. Garcia, T. Lischke, and S. Marburger, Valence and C 1s core level photoelectron spectra of camphor, J. Electron Spectrosc. Relat. Phenom. 125, 197 (2002).
  37. I. Powis, C. J. Harding, G. A. Garcia, and L. Nahon, A valence photoelectron imaging investigation of chiral asymmetry in the photoionization of fenchone and camphor, Chem. Phys. Chem. 9, 475 (2008).
  38. R. Hadidi, D. K. Bozanic, G. A. Garcia, and L. Nahon, Electron asymmetries in the photoionization of chiral molecules: Possible astrophysical implications, Adv. Phys. X 3, 1477530 (2018).
  39. S. Y. Buhmann, L. Knöll, D.-G. Welsch, and H. T. Dung, Casimir-Polder forces: A nonperturbative approach, Phys. Rev. A 70, 052117 (2004).

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Phys. Rev. Lett. 134, 253001– Published 24 June, 2025
  • Received 4 December 2024
  • Revised 24 February 2025
  • Accepted 29 May 2025
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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.

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