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Coupled electron-nuclear dynamics in resonant 1σ→2π x-ray Raman scattering of CO molecules

Couto, Rafael C.; Guarise, Marco; Nicolaou, Alessandro; Jaouen, Nicolas; Chiuzbǎian, Gheorghe S.; Lüning, Jan; Ekholm, Victor; Rubensson, Jan Erik; Såthe, Conny LU and Hennies, Franz LU , et al. (2016) In Physical Review A (Atomic, Molecular and Optical Physics) 93(3).
Abstract

We present a detailed experimental-theoretical analysis of O K-edge resonant 1σ-2π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Πx1 and Πy1 core-excited states of CO.... (More)

We present a detailed experimental-theoretical analysis of O K-edge resonant 1σ-2π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Πx1 and Πy1 core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the |4σ-12π1) final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.

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Contribution to journal
publication status
published
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Physical Review A (Atomic, Molecular and Optical Physics)
volume
93
issue
3
publisher
American Physical Society
external identifiers
  • Scopus:84961724217
ISSN
1050-2947
DOI
10.1103/PhysRevA.93.032510
language
English
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yes
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cac4f31e-fc1c-4206-8a67-16270c017672
date added to LUP
2016-07-11 12:04:48
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2016-07-11 12:04:48
@misc{cac4f31e-fc1c-4206-8a67-16270c017672,
  abstract     = {<p>We present a detailed experimental-theoretical analysis of O K-edge resonant 1σ-2π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Πx1 and Πy1 core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the |4σ-12π1) final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.</p>},
  author       = {Couto, Rafael C. and Guarise, Marco and Nicolaou, Alessandro and Jaouen, Nicolas and Chiuzbǎian, Gheorghe S. and Lüning, Jan and Ekholm, Victor and Rubensson, Jan Erik and Såthe, Conny and Hennies, Franz and Guimarães, Freddy F. and Ågren, Hans and Gel'Mukhanov, Faris and Journel, Loïc and Simon, Marc and Kimberg, Victor},
  issn         = {1050-2947},
  language     = {eng},
  month        = {03},
  number       = {3},
  publisher    = {ARRAY(0x8e3b718)},
  series       = {Physical Review A (Atomic, Molecular and Optical Physics)},
  title        = {Coupled electron-nuclear dynamics in resonant 1σ→2π x-ray Raman scattering of CO molecules},
  url          = {http://dx.doi.org/10.1103/PhysRevA.93.032510},
  volume       = {93},
  year         = {2016},
}