Title: An experimental and theoretical study of the C 1s ionization satellites in CH ₃I

Abstract

We report the C 1s ionization spectrum of CH ₃I has been studied both experimentally and theoretically. Synchrotron radiation has been employed to record polarization dependent photoelectron spectra at a photon energy of 614 eV. These spectra encompass the main-line due to the C 1s single-hole state and the peaks associated with the shake-up satellites. Vertical ionization energies and relative photoelectron intensities have been computed using the fourth-order algebraic-diagrammatic construction approximation scheme for the one-particle Green’s function and the 6-311++G** basis set. The theoretical spectrum derived from these calculations agrees qualitatively with the experimental results, thereby allowing the principal spectral features to be assigned. According to our calculations, two ²A ₁ shake-up states of the C 1s ^-1 σ _CI → σ$$*\atop{CI}$$ type with singlet and triplet intermediate coupling of the electron spins (S' = 0, 1) play an important role in the spectrum and contribute significantly to the overall intensity. Both of these states are expected to have dissociative diabatic potential energy surfaces with respect to the C–I separation. Whereas the upper of these states perturbs the manifold of Rydberg states, the lower state forms a band which is characterized by a strongly increased width. Our results indicate that the lowest shake-up peak with significant spectral intensity is due to the pair (S' = 0, 1) of ²E (C 1s ^-1 I 5p → σ$$*\atop{CI}$$) states. We predict that these ²E states acquire photoelectron intensity due to spin-orbit interaction. Lastly, such interactions play an important role here due to the involvement of the I 5p orbitals.

Authors:

Trofimov, A. B.  ^[1];

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Belogolova, A. M. ^[1]; Serebrennikova, S. A. ^[2]; Forbes, R. ^[3]; Pratt, S. T.  ^[4];

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Holland, D. M. P.  ^[5]

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+ Show Author Affiliations

1. Irkutsk State Univ. (Russia); Favorsky’s Institute of Chemistry, SB RAS, Irkutsk (Russia)
2. Irkutsk State Univ. (Russia)
3. Univ. College London, Bloomsbury (United Kingdom); Univ. of Ottawa, Ontario (Canada)
4. Argonne National Lab. (ANL), Lemont, IL (United States)
5. Daresbury Lab. (United Kingdom)

Publication Date:

2019-06-11

Research Org.:

SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE; Ministry of Education and Science of the Russian Federation; Science and Technology Facilities Council

OSTI Identifier:

1546955

Alternate Identifier(s):

OSTI ID: 1525558; OSTI ID: 1559562

Grant/Contract Number:  

AC02-76SF00515; AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 150; Journal Issue: 22; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS