Rotational dependence of the Rydberg–valence interactions in the 1Πg states of molecular oxygen
- 1 February 1991
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 94 (3), 1705-1711
- https://doi.org/10.1063/1.459942
Abstract
The two‐photon d 1Πg(v’)← ←X 3Σ−g(v‘) transition in O2 is studied using resonance enhanced multiphoton ionization (REMPI) spectroscopy and the lowest four vibrational levels of the d 1Πg Rydberg state are characterized. Anomalies in the rotational constants of the Rydberg vibrational levels and perturbations in the REMPI spectra are attributed to the interaction of the Rydberg state with a bound diabatic 1Πg valence state. The rotational dependence of the Rydberg–valence interaction is explored by solving the coupled eigenvalue equations describing the interaction of the two states. The results from solution of the coupled equations as well as observations from photoelectron spectroscopy experiments are used to understand the additional structure seen in the REMPI spectra in the vicinity of the v’=2 Rydberg vibrational level.Keywords
This publication has 9 references indexed in Scilit:
- On the numerical solution of coupled eigenvalue differential equations arising in molecular spectroscopyComputer Physics Communications, 1990
- Dissociation dynamics of the d 1Πg and C 3Πg v=0–2 vibrational states in O2The Journal of Chemical Physics, 1989
- Comment on: ‘‘Predissociation of the d 1Πg Rydberg state in O2: Nature of the Rydberg–valence interactions’’The Journal of Chemical Physics, 1989
- Predissociation of the d 1Πg Rydberg state in O2: Nature of the Rydberg–valence interactionsThe Journal of Chemical Physics, 1988
- Two photon resonance enhanced multiphoton ionization spectroscopy of gas phase O2 a 1Δg between 305–350 nmThe Journal of Chemical Physics, 1987
- Photoelectron spectroscopy of the excited states of the CH radicalThe Journal of Chemical Physics, 1986
- Optical spectra of the lowest Πg Rydberg states in O2The Journal of Chemical Physics, 1985
- Electron energy-loss studies of molecular oxygen in the region 6.0-16.1 eV using a multidetector electron spectrometerJournal of Physics B: Atomic and Molecular Physics, 1983
- A b i n i t i o configuration interaction study of the valence states of O2The Journal of Chemical Physics, 1977