A perturbation theory guide to open-shell complexes: OH--Ar( X sup 2. Pi. )

Journal Article · Fri Feb 14 23:00:00 EST 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.462008· OSTI ID:5133183

Green, Jr, W H; Lester, M I ^[1]

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1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States)

Perturbation theory is used to understand the experimentally observed stimulated emission spectra of OH--Ar({ital X} {sup 2}{Pi}). A useful zero-order Hamiltonian for an open-shell van der Waals complex is presented, and the most important perturbation terms are identified: rotational decoupling ( {ital j}{center dot}{ital s}), Renner--Teller coupling ({ital {cflx V}}{sub 2}), and a Coriolis interaction ({ital J}{center dot}{ital j}). This treatment reveals those parts of the Hamiltonian which are responsible for various unusual features in the spectra of open-shell complexes, such as the large parity splittings in certain vibrational bands and spin--orbit--induced predissociation of the OH--Ar({ital X} {sup 2}{Pi}) complex. The magnitude of the parity splitting is shown to be directly proportional to the change in the intermolecular potential when the odd electron in the free radical lies in or out of the O--H--Ar plane, the {ital A}{prime} and {ital A}{double prime} surfaces. The measured splitting is used to infer the magnitude of the difference between the {ital A}{prime} and {ital A}{double prime} potential-energy surfaces ({similar to}12 cm{sup {minus}1}) in the region sampled by the first excited bend.

• OSTI ID: 5133183
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 96:4; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664100* -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ARGON COMPLEXES
COMPLEXES
CORIOLIS FORCE
COUPLING
DECOUPLING
DISSOCIATION
EMISSION
EMISSION SPECTRA
ENERGY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
HAMILTONIANS
HYDROGEN COMPOUNDS
HYDROXIDES
INTERMEDIATE COUPLING
L-S COUPLING
MATHEMATICAL OPERATORS
OXYGEN COMPOUNDS
PARITY
PARTICLE PROPERTIES
PERTURBATION THEORY
POTENTIAL ENERGY
PREDISSOCIATION
QUANTUM OPERATORS
ROTATIONAL STATES
SPECTRA
STIMULATED EMISSION
VAN DER WAALS FORCES
VIBRATIONAL STATES