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Resonant inelastic x-ray scattering and photoemission measurement of O2 : Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1 s → Rydberg states

Gejo, T. ; Oura, M. ; Tokushima, T. LU ; Horikawa, Yuka ; Arai, H. ; Shin, S. ; Kimberg, V. and Kosugi, N. (2017) In Journal of Chemical Physics 147(4).
Abstract

High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ∗ energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also... (More)

High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ∗ energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O) from O2 excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O∗ has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states.

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publishing date
type
Contribution to journal
publication status
published
in
Journal of Chemical Physics
volume
147
issue
4
article number
044310
publisher
American Institute of Physics (AIP)
external identifiers
  • pmid:28764346
  • scopus:85026498654
ISSN
0021-9606
DOI
10.1063/1.4994895
language
English
LU publication?
no
additional info
Publisher Copyright: © 2017 Author(s).
id
ed137423-e288-43ab-89a7-59c367b1cb55
date added to LUP
2023-03-02 20:11:27
date last changed
2024-04-18 19:12:54
@article{ed137423-e288-43ab-89a7-59c367b1cb55,
  abstract     = {{<p>High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ∗ energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O<sub>2</sub>. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O) from O<sub>2</sub> excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O∗ has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states.</p>}},
  author       = {{Gejo, T. and Oura, M. and Tokushima, T. and Horikawa, Yuka and Arai, H. and Shin, S. and Kimberg, V. and Kosugi, N.}},
  issn         = {{0021-9606}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{4}},
  publisher    = {{American Institute of Physics (AIP)}},
  series       = {{Journal of Chemical Physics}},
  title        = {{Resonant inelastic x-ray scattering and photoemission measurement of O<sub>2</sub> : Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1 s → Rydberg states}},
  url          = {{http://dx.doi.org/10.1063/1.4994895}},
  doi          = {{10.1063/1.4994895}},
  volume       = {{147}},
  year         = {{2017}},
}