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Orbital evolution and promotion effects in the photoionization dynamics of ^2Σ^− Rydberg states of OH

Stephens, J. A. and McKoy, V. (1990) Orbital evolution and promotion effects in the photoionization dynamics of ^2Σ^− Rydberg states of OH. Journal of Chemical Physics, 93 (11). pp. 7863-7873. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20151028-114732414

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.459368DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/93/11/10.1063/1.459368PublisherArticle
Alternate Title:Orbital evolution and promotion effects in the photoionization dynamics of 2Σ− Rydberg states of OH
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.
Funders:
Funding AgencyGrant Number
NSFCHE-8521391
Air Force Office of Scientific Research (AFOSR)87-0039
Department of Energy (DOE)DE-FG03-87ER60513
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Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics8172
Issue or Number:11
Record Number:CaltechAUTHORS:20151028-114732414
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151028-114732414
Official Citation:Orbital evolution and promotion effects in the photoionization dynamics of 2Σ− Rydberg states of OH Stephens, J. A. and McKoy, V., The Journal of Chemical Physics, 93, 7863-7873 (1990), DOI:http://dx.doi.org/10.1063/1.459368
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61648
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:09 Nov 2015 23:54
Last Modified:03 Oct 2019 09:10

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