Spin–orbit and electronic autoionization in HCl

Journal Article · Fri Jan 01 00:00:00 EST 1988 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.454159· OSTI ID:5513416

Lefebvre-Brion, H. ^[1]; Dehmer, Patricia M. ^[2]; Chupka, W. A. ^[3]

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1. Univ. Paris-Sud, Orsay (France)
2. Argonne National Lab. (ANL), Argonne, IL (United States)
3. Yale Univ., New Haven, CT (United States)

The high resolution relative photoionization cross section for HCl is reported in the wavelength region 720--975 Â. In addition, results of calculations are presented for spin--orbit autoionization in the energy region between the X ²Π_3/2 and X ²Π_1/2 ionization thresholds and for electrostatic autoionization in the energy region containing Rydberg series converging to the A ²Σ⁺ excited ionic state. For the case of spin--orbit autoionization in the region just above the X ²Π_3/2 ionic threshold, it is found that the energy positions of the first peaks are approximately correct if the ionization potential is modified by ≅80 cm⁻¹; however the intensities of the peaks are strongly perturbed, most probably by high lying vibrational levels of the V ¹Σ⁺ valence state. In the wavelength region 780--930 Â, two progressions of Rydberg states converging to the A ²Σ⁺ excited ionic state and autoionized by electrostatic interaction are also studied by a b i n i t i o multichannel quantum defect theory. Qualitative agreement with the experimental data is obtained by a slight adjustment of some quantum defects, the other parameters being those obtained by a b i n i t i o calculations. Comparison with the absorption spectra of both HCl and DCl is also made. Progression I of Terwilliger and Smith (J. Chem. Phys 6 3, 1008 (1975)] is reassigned to the (A ²Σ⁺) 3dπ ¹Π state and progression II to the (A ²Σ⁺) 3pπ ¹Π state on which is superimposed the (A ²Σ⁺) 3dσ ¹Σ⁺ state. The large difference between the quantum defects of dπ and dσ states precludes the existence of a 3d complex..

• Research Organization: Laboratoire de Photophysique Moleculaire, Bat. 213, Universite de Paris-Sud, 91405 Orsay, France
• Sponsoring Organization: USDOE; Office of Health and Environmental Research (OHER); US Department of the Navy, Office of Naval Research (ONR)
• DOE Contract Number: W-31-109-ENG-38
• OSTI ID: 5513416
• Journal Information: Journal of Chemical Physics, Vol. 88, Issue 2; ISSN 0021-9606: JCPSA6
• Publisher: American Institute of Physics (AIP)
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
HYDROCHLORIC ACID
ABSORPTION SPECTRA
AUTOIONIZATION
PHOTOIONIZATION
ELECTRONIC STRUCTURE
L-S COUPLING
COUPLING
HYDROGEN COMPOUNDS
INORGANIC ACIDS
INTERMEDIATE COUPLING
IONIZATION
SPECTRA
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory