Orbital evolution and promotion effects in the photoionization dynamics of sup 2. Sigma. sup minus Rydberg states of OH

Journal Article · Sat Dec 01 04:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459368· OSTI ID:6046251

Stephens, J A; McKoy, V ^[1]

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1. Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA (USA)

In this paper, we discuss the photoionization dynamics of the {ital D} {sup 2}{Sigma}{sup {minus}}(1{pi}{sup 2}3{ital p}{sigma}) and 3 {sup 2}{Sigma}{sup {minus}}(1{pi}{sup 2}4{ital s}{sigma}) 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 {ital D} {sup 2}{Sigma}{sup {minus}}(1{pi}{sup 2}5{sigma}) and 3 {sup 2}{Sigma}{sup {minus}}(1{pi}{sup 2}6{sigma}) 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.

• DOE Contract Number: FG03-87ER60513
• OSTI ID: 6046251
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 93:11; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ANGULAR DISTRIBUTION
BRANCHING RATIO
DISTRIBUTION
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
HYDROXYL RADICALS
IONIZATION
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
RADICALS
RESOLUTION
ROTATIONAL STATES
RYDBERG STATES
SPECTROSCOPY
VIBRATIONAL STATES