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Site-resolved recoil-induced asymmetry of nondipole molecular-frame photoelectron angular distributions in inner-shell photoionization of CO by 20 keV photons
Phys. Rev. A 113, 053112 – Published 20 May, 2026
DOI: https://doi.org/10.1103/1fkh-q31m
Abstract
Angular distributions of K-shell photoelectrons from CO molecules ionized by 20 keV photons are studied experimentally and theoretically in the molecular frame of reference. At this high photon energy, nondipole contributions to the light-matter interaction induce a strong forward-directed emission of the photoelectrons, which is only slightly modulated by scattering from the molecular potential. In addition, we observe a recently predicted asymmetry in the photoelectron emission distributions with respect to the polarization direction [Phys. Rev. Lett. 123, 243201 (2019)], which is caused by a rotational recoil of the nuclei imposed by the fast photoelectrons and high-energy photons. By addressing the C and O atoms separately in CO, we are able to resolve the molecular site that experiences this rotational kick, which was not possible in the previous study of molecules. Our experimental results are explained by ab initio electronic structure calculations augmented by a semiclassical modeling of the rotational-recoil effect.
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References (42)
- M. Simon, M. N. Piancastelli, and D. W. Lindle, Hard-X-ray photoelectron spectroscopy of atoms and molecules, in Hard X-ray Photoelectron Spectroscopy (HAXPES), edited by J. C. Woicik (Springer, Cham, 2016), pp. 65–110.
- ID31–High-energy beamline for buried interface structure and materials processing of the European Synchrotron Radiation Facility (ESRF) in Grenoble, France, https://www.esrf.fr/UsersAndScience/Experiments/StructMaterials/ID31.
- J. Ullrich, A. Rudenko, and R. Moshammer, Free-electron lasers: New avenues in molecular physics and photochemistry, Annu. Rev. Phys. Chem. 63, 635 (2012).
- D. W. Lindle and O. Hemmers, Breakdown of the dipole approximation in soft-X-ray photoemission, J. Electron. Spectrosc. Relat. Phenom. 100, 297 (1999).
- R. W. Dunford, E. P. Kanter, B. Krässig, S. H. Southworth, and L. Young, Higher-order processes in X-ray photoionization and decay, Radiat. Phys. Chem. 70, 149 (2004).
- I. E. Brumboiu, O. Eriksson, and P. Norman, Atomic photoionization cross sections beyond the electric dipole approximation, J. Chem. Phys. 150, 044306 (2019).
- M. Schmidt, N. Melzer, M. Kircher, G. Kastirke, A. Pier, L. Kaiser, P. Daum, D. Tsitsonis, M. Astaschov, J. Rist, N. Anders, P. Roth, K. Lin, J. Drnec, F. Trinter, M. S. Schöffler, L. P. H. Schmidt, N. M. Novikovskiy, P. V. Demekhin, T. Jahnke, et al., Role of the binding energy on nondipole effects in single-photon ionization, Phys. Rev. Lett. 132, 233002 (2024).
- S. Grundmann, M. Kircher, I. Vela-Perez, G. Nalin, D. Trabert, N. Anders, N. Melzer, J. Rist, A. Pier, N. Strenger, J. Siebert, P. V. Demekhin, L. P. H. Schmidt, F. Trinter, M. S. Schöfler, T. Jahnke, and R. Dörner, Observation of photoion backward emission in photoionization of He and , Phys. Rev. Lett. 124, 233201 (2020).
- W. Domcke and L. S. Cederbaum, Electronic recoil effects in high-energy photoelectron spectroscopy, J. Electron Spectrosc. Relat. Phenom. 13, 161 (1978).
- T. D. Thomas, E. Kukk, H. Fukuzawa, K. Ueda, R. Püttner, Y. Tamenori, T. Asahina, N. Kuze, H. Kato, M. Hoshino, H. Tanaka, M. Meyer, J. Plenge, A. Wirsing, E. Serdaroglu, R. Flesch, E. Rühl, S. Gavrilyuk, F. Gemukhanov, and A. Lindblad, Photoelectron-recoil-induced rotational excitation of the state in , Phys. Rev. A 79, 022506 (2009).
- D. Céolin, J.-C. Liu, V. Vaz da Cruz, H. Ågren, L. Journel, R. Guillemin, T. Marchenko, R. K. Kushawaha, M. N. Piancastelli, R. Püttner, M. Simon, and F. Gemukhanov, Recoil-induced ultrafast molecular rotation probed by dynamical rotational Doppler effect, Proc. Natl. Acad. Sci. USA 116, 4877 (2019).
- M. Simon, R. Püttner, T. Marchenko, R. Guillemin, R. K. Kushawaha, L. Journel, G. Goldsztejn, M. N. Piancastelli, J. M. Ablett, J.-P. Rueff, and D. Céolin, Atomic Auger Doppler effects upon emission of fast photoelectrons, Nat. Commun. 5, 4069 (2014).
- E. Kukk, T. D. Thomas, D. Céolin, S. Granroth, O. Travnikova, M. Berholts, T. Marchenko, R. Guillemin, L. Journel, I. Ismail, R. Püttner, M. N. Piancastelli, K. Ueda, and M. Simon, Energy transfer into molecular vibrations and rotations by recoil in inner-shell photoemission, Phys. Rev. Lett. 121, 073002 (2018).
- E. Kukk, K. Ueda, U. Hergenhahn, X.-J. Liu, G. Prümper, H. Yoshida, Y. Tamenori, C. Makochekanwa, T. Tanaka, M. Kitajima, and H. Tanaka, Violation of the Franck-Condon principle due to recoil effects in high energy molecular core-level photoionization, Phys. Rev. Lett. 95, 133001 (2005).
- T. D. Thomas, E. Kukk, R. Sankari, H. Fukuzawa, G. Prümper, K. Ueda, R. Püttner, J. Harries, Y. Tamenori, T. Tanaka, M. Hoshino, and H. Tanaka, Recoil excitation of vibrational structure in the carbon photoelectron spectrum of , J. Chem. Phys. 128, 144311 (2008).
- K. Kreidi, P. V. Demekhin, T. Jahnke, T. Weber, T. Havermeier, X.-J . Liu, Y. Morisita, S. Schössler, L. P. H. Schmidt, M. Schöffler, M. Odenweller, N. Neumann, L. Foucar, J. Titze, B. Ulrich, F. Sturm, C. Stuck, R. Wallauer, S. Voss, I. Lauter, et al., Photo- and Auger-electron recoil induced dynamics of interatomic Coulombic decay, Phys. Rev. Lett. 103, 033001 (2009).
- J. Weiherer, N. Melzer, M. Kircher, A. Pier, L. Kaiser, J. Kruse, N. Anders, J. Stindl, L. Sommerlad, O. D. McGinnis, M. Schmidt, J. Drnec, F. Trinter, M. S. Schoffler, L. Ph. H. Schmidt, N. Sisourat, S. Eckart, T. Jahnke, and R. Dörner, Selective bond breaking in induced by photoelectron recoil, Phys. Rev. Lett. 135, 113002 (2025).
- M. Kircher, J. Rist, F. Trinter, S. Grundmann, M. Waitz, N. Melzer, I. Vela-Perez, T. Mletzko, A. Pier, N. Strenger, J. Siebert, R. Janssen, V. Honkimäki, J. Drnec, P. V. Demekhin, L. P. H. Schmidt, M. S. Schöffler, T. Jahnke, and R. Dörner, Photon-momentum-induced molecular dynamics in photoionization of at keV, Phys. Rev. Lett. 123, 193001 (2019).
- M. Kircher, J. Rist, F. Trinter, S. Grundmann, M. Waitz, N. Melzer, I. Vela-Peréz, T. Mletzko, A. Pier, N. Strenger, J. Siebert, R. Janssen, L. P. H. Schmidt, A. N. Artemyev, M. S. Schöffler, T. Jahnke, R. Dörner, and P. V. Demekhin, Recoil-induced asymmetry of nondipole molecular frame photoelectron angular distributions in the hard X-ray regime, Phys. Rev. Lett. 123, 243201 (2019).
- R. N. Zare, Photoejection dynamics, Mol. Photochem. 4, 1 (1972).
- L. Ph H. Schmidt, J. Lower, T. Jahnke, S. Schö, M. S. Schöffler, A. Menssen, C. Lév, N. Sisourat, R. Ta, H. Schmidt-Böcking, and R. Dörner, Momentum transfer to a free floating double slit: Realization of a thought experiment from the Einstein-Bohr debates, Phys. Rev. Lett. 111, 103201 (2013).
- R. Dörner, V. Mergel, O. Jagutzki, L. Spielberger, J. Ullrich, R. Moshammer, and H. Schmidt-Böcking, Cold target recoil ion momentum spectroscopy: A ‘momentum microscope’ to view atomic collision dynamics, Phys. Rep. 330, 95 (2000).
- J. Ullrich, R. Moshammer, A. Dorn, R. Dörner, L. Ph. H. Schmidt, and H. Schmidt-Böcking, Recoil-ion and electron momentum spectroscopy: Reaction-microscopes, Rep. Prog. Phys. 66, 1463 (2003).
- T. Jahnke, Th. Weber, T. Osipov, A. L. Landers, O. Jagutzki, L. Ph. H. Schmidt, C. L. Cocke, M. H. Prior, H. Schmidt-Böcking, and R. Dörner, Multicoincidence studies of photo and Auger electrons from fixed-in-space molecules using the COLTRIMS technique, J. Electron Spectrosc. Relat. Phenom. 141, 229 (2004).
- G. B. M. Vaughan, J. P. Wright, A. Bytchkov, M. Rossat, H. Gleyzolle, I. Snigireva, and A. Snigirev, X-ray transfocators: Focusing devices based on compound refractive lenses, J. Synchrotron Radiat. 18, 125 (2011).
- O. Jagutzki, A. Cerezo, A. Czasch, R. Dörner, M. Hattaß, M. Huang, V. Mergel, U. Spillmann, K. Ullmann-Pfleger, T. Weber, H. Schmidt-Böcking, and G. D. W. Smith, Multiple hit readout of a microchannel plate detector with a three-layer delay-line anode, IEEE Trans. Nucl. Sci. 49, 2477 (2002).
- R. Dörner, V. Mergel, L. Spielberger, M. Achler, Kh. Khayyat, T. Vogt, H. Bräuning, O. Jagutzki, T. Weber, J. Ullrich, R. Moshammer, M. Unverzagt, W. Schmitt, H. Khemliche, M. H. Prior, C. L. Cocke, J. Feagin, R. E. Olson, and H. Schmidt-Böcking, Kinematically complete experiments using cold target recoil ion momentum spectroscopy, Nucl. Instrum. Methods Phys. Res. Sect. B 124, 225 (1997).
- N. Melzer, M. Kircher, A. Pier, L. Kaiser, J. Kruse, N. Anders, J. Stindl, L. Sommerlad, D. McGinnis, M. Schmidt, L. Nowak, A. Kügler, I. Dwojak, J. Drnec, F. Trinter, M. S. Schöffler, L. P. H. Schmidt, N. M. Novikovskiy, P. V. Demekhin, T. Jahnke, and R. Dorner, Role of the Coulomb potential in Compton scattering, Phys. Rev. Lett. 133, 183002 (2024).
- D. M. Haubenreißer, N. M. Novikovskiy, N. Melzer, M. Kircher, A. Pier, L. Kaiser, J. Kruse, N. Anders, J. Stindl, L. Sommerlad, O. D. McGinnis, M. Schmidt, L. Nowak, A. Kügler, I. Dwojak, J. Drnec, F. Trinter, M. S. Schöffler, L. P. H. Schmidt, T. Jahnke, et al., Electron diffraction imaging of carbon monoxide via ionization by Compton scattering of 20 keV photons, Phys. Rev. Lett. 135, 033203 (2025).
- Ph V. Demekhin, A. Ehresmann, and V. L. Sukhorukov, Single center method: A computational tool for ionization and electronic excitation studies of molecules, J. Chem. Phys. 134, 024113 (2011).
- V. Ph. Demekhin, D. V. Omelyanenko, B. M. Lagutin, V. L. Sukhorukov, L. Werner, A. Ehresmann, K.-H. Schartner, and H. Schmoranzer, Investigation of photoionization and photodissociation of an oxygen molecule by the method of coupled differential equations, Opt. Spectrosc. 102, 318 (2007).
- N. M. Novikovskiy, A. N. Artemyev, D. V. Rezvan, B. M. Lagutin, and Ph. V. Demekhin, Multichannel single center method, J. Phys. B: At. Mol. Opt. Phys. 55, 175001 (2022).
- D. V. Rezvan, K. Klyssek, S. Grundmann, A. Pier, N. M. Novikovskiy, N. Strenger, D. Tsitsonis, M. Kircher, I. Vela-Peréz, K. Fehre, F. Trinter, M. S. Schöffler, T. Jahnke, R. Dörner, and P. V. Demekhin, Observation of nondipole-induced asymmetry in the angular emission distribution of photoelectrons from fixed-in-space CO molecules, Phys. Rev. Lett. 129, 253201 (2022).
- K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Springer, New York, 1979).
- M. W. Schmidt, K. K. Baldrige, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, Jr., General atomic and molecular electronic structure system, J. Comput. Chem. 14, 1347 (1993).
- T. H. Dunning, Jr., Gaussian basis functions for use in molecular calculations. III. Contraction of () atomic basis sets for the first-row atoms, J. Chem. Phys. 55, 716 (1971).
- V. Myrseth, J. D. Bozek, E. Kukk, L. J. Sæthre, and T. D. Thomas, Adiabatic and vertical carbon ionization energies in representative small molecules, J. Electron Spectrosc. Relat. Phenom. 122, 57 (2002).
- P. Wang, T. X. Carroll, T. D. Thomas, L. J. Sæthre, and K. J. Børve, Calibration of oxygen ionization energies. Accurate energies for , , CO, and , J. Electron Spectrosc. Relat. Phenom. 251, 147103 (2021).
- K. C. Prince, M. Vondrácek, J. Karvonen, M. Coreno, R. Camilloni, L. Avaldi, and M. de Simone, A critical comparison of selected and core hole widths, J. Electron Spectrosc. Relat. Phenom. 101–103, 141 (1999).
- G. Kastirke, M. S. Schöffler, M. Weller, J. Rist, R. Boll, N. Anders, T. M. Baumann, S. Eckart, B. Erk, A. De Fanis, K. Fehre, A. Gatton, S. Grundmann, P. Grychtol, A. Hartung, M. Hofmann, M. Ilchen, C. Janke, M. Kircher, M. Kunitski, et al., Photoelectron diffraction imaging of a molecular breakup using an X-ray free-electron laser, Phys. Rev. X 10, 021052 (2020).
- I. Vela-Peréz, F. Ota, A. Mhamdi, Y. Tamura, J. Rist, N. Melzer, S. Uerken, G. Nalin, N. Anders, D. You, M. Kircher, C. Janke, M. Waitz, F. Trinter, R. Guillemin, M. N. Piancastelli, M. Simon, V. T. Davis, J. B. Williams, R. Dörner, et al., High-energy molecular-frame photoelectron angular distributions: A molecular bond-length ruler, Phys. Chem. Chem. Phys. 25, 13784 (2023).
- N. Anders, C. Braun, R. Doerner, I. Dwojak, T. Jahnke, L. Kaiser, M. Kircher, J. Kruse, M. A. Kügler, O. D. McGinnis, N. Melzer, L. Nowak, A. Pier, L. Schmidt, M. Schmidt, L. Sommerlad, J. Stindl, and F. Trinter, Investigating molecular-frame Compton electron angular distributions in CO [Dataset], European Synchrotron Radiation Facility, 2026, https://doi.org/10.15151/ESRF-ES-1299363304.