Orbital evolution and promotion effects in the photoionization dynamics of ^2Σ^− Rydberg states of OH
- Creators
- Stephens, J. A.
- McKoy, V.
Abstract
In this paper, we discuss the photoionizationdynamics of the D ^2Σ^−(1π^23pσ) and 3 ^2Σ^−(1π^24sσ) Rydberg states of OH, emphasizing the critical role that Rydberg orbital evolution plays at intermediate to larger internuclear distances in determining vibrational and rotational molecular ion distributions. The orbital evolution process is discussed in terms of diabatic and adiabatic molecular states, united atom–separated atom correlation rules, and quantum defect functions. Vibrationally resolved photoelectron spectra and angular distributions for resonance enhanced multiphoton ionization (REMPI) of OH via the D ^2Σ^−(1π^25σ) and 3 ^2Σ^−(1π^26σ) Rydberg states are considered as examples. The results and conclusions are relevant to vibrationally and rotationally resolved REMPI studies of all first‐row molecular hydrides, due to the similarity of their electronic structure and correspondence to their associated united atom.
Additional Information
© 1990 American Institute of Physics. (Received 16 July 1990; accepted 29 August 1990) We thank Dr. Helene Levebvre-Brion for pointing out Refs. 24 and 25 and for a helpful discussion and encouragement. One of us thanks Dr. Michael Cavagnero for pointing out Ref. 45 and a helpful discussion and Dr. K. T. Lu for a helpful discussion on quantum defect functions. Finally, we thank Dr. Ewine van Dishoeck for providing numerical values of the potential energy curves from her publications. This work was supported by grants from the National Science Foundation (CHE-8521391), Air Force Office of Scientific Research (Contract No. 87-0039), and the Office of Health and Environmental Research of the U. S. Department of Energy (DE-FG03-87ER60513). We also acknowledge use of resources of the San Diego SuperComputer Center, which is supported by the National Science Foundation.Attached Files
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Additional details
- Alternative title
- Orbital evolution and promotion effects in the photoionization dynamics of 2Σ− Rydberg states of OH
- Eprint ID
- 61648
- Resolver ID
- CaltechAUTHORS:20151028-114732414
- NSF
- CHE-8521391
- Air Force Office of Scientific Research (AFOSR)
- 87-0039
- Department of Energy (DOE)
- DE-FG03-87ER60513
- Created
-
2015-11-09Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 8172