Autoionization structure and rotational contours in the multiphoton ionization spectrum of carbon dioxide

Journal Article · Tue Jan 15 00:00:00 EST 1991 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459976· OSTI ID:6203965

Johnson, P; Wu, M ^[1]

---

1. Department of Chemistry, State University of New York, Stony Brook, New York 11794 (US)

The structure of the multiphoton ionization spectra of carbon dioxide in the vicinity of 4{ital f} and 5{ital f} resonances is analyzed in detail. The rotational contour of the {ital f} complex is calculated using the frame transform method of Chang and Fano. It is found that only one electronic splitting constant {ital k}{sub 4{ital f}}=7 cm{sup {minus}1} is needed to attain a reasonable approximation to the experimental spectrum. This would indicate that the Rydberg electron is relatively atomic-like and excluded from the core. It is also found that the dominant contribution to the three-photon excitation strength comes from the {Delta}{Omega}=3 path. The additional sharp structure to the blue of the 4{ital f} and 5{ital f} resonances is due to four-photon resonances with autoionization states belonging to Rydberg series converging on the {ital {tilde A}} and {ital {tilde B}} states of the ion. The unusual strength of these lines arises from a coincidence between the photon energy and the energy of {ital {tilde B}}{l arrow}{ital {tilde X}} core transitions and the predissociation of the nearby bound resonances, which limits their strength.

• DOE Contract Number: FG02-86ER13590
• OSTI ID: 6203965
• Journal Information: Journal of Chemical Physics; (USA), Vol. 94:2; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON DIOXIDE
PHOTOIONIZATION
ABSORPTION SPECTRA
AUTOIONIZATION
L-S COUPLING
MULTI-PHOTON PROCESSES
PREDISSOCIATION
RESONANCE
ROTATIONAL STATES
RYDBERG STATES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COUPLING
DISSOCIATION
ENERGY LEVELS
EXCITED STATES
INTERMEDIATE COUPLING
IONIZATION
OXIDES
OXYGEN COMPOUNDS
SPECTRA
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory
400201 - Chemical & Physicochemical Properties