Effects of vibronic interaction and autoionization on the photoelectron spectrum of N/sub 2/O

Journal Article · Tue Jul 01 04:00:00 EDT 1980 · J. Chem. Phys.; (United States)

OSTI ID:5363307

Dehmer, P M; Dehmer, J L; Chupka, W A

High-resolution and high-sensitivity HeI photoelectron spectra (PES) are reported for the first four valence levels of N/sub 2/O. The vibrational structure, including many new peaks, is completely assigned for the X /sup 2/Pi, A /sup 2/..sigma../sup +/, and C /sup 2/..sigma../sup +/ electronic states, and in all three cases excitation of a single quantum of the bending vibration is observed. The bending mode appears as a result of vibronic coupling within and between different electronic states. The Renner--Teller splitting is resolved in the (0,1,0) band of the transition to the X /sup 2/Pi state. The relative intensities of the vibrational bands in the X /sup 2/Pi and A /sup 2/..sigma../sup +/ states are compared to the intensities determined from the threshold photoelectron spectra (TPES) of Frey et al. (Chem. Phys. Lett. 54, 411 (1978)). In both states, autoionization of intermediate neutral states that are nearly degenerate with the molecular ion state to which they decay increases the relative intensities of the higher vibrational bands in the TPES. This resonant autoionization process can enhance bands selectively, and, in particular, the higher quanta of the symmetric stretch are systematically more intense in the TPES than in the HeI PES. New relative photoionization cross sections for N/sub 2/O and its fragment ions are presented which show that even weak autoionization features can have a substantial effect on the intensities in the TPES.

• Research Organization: Argonne National Laboratory, Argonne, Illinois 60439
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5363307
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
AUTOIONIZATION
CHALCOGENIDES
CROSS SECTIONS
ELECTRON SPECTROSCOPY
IONIZATION
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROUS OXIDE
OXIDES
OXYGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
RESOLUTION
SPECTROSCOPY