Electronic spectroscopy of the ArOH and ArOD complexes

Journal Article · Sun Jan 14 23:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.458125· OSTI ID:6904063

Fawzy, W M; Heaven, M C ^[1]

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1. Department of Chemistry, Emory University, Atlanta, Georgia 30322 (USA)

Laser induced fluorescence spectra of the ArOH bands associated with electronic excitation of the OH {ital A}--{ital X}({ital v}{prime}=0{minus}{ital v}{double prime}=0) transition were reported previously. An extensive search in the vicinity of the OH/OD {ital A} ({sup 2}{Sigma}{sup +}){minus}{ital X}({sup 2}{Pi}) system ({ital v}{prime}=0{minus}{ital v}{double prime}=0) and ({ital v}{prime}=1{minus}{ital v}{double prime}=0) led to the observation of 36 vibronic bands which were identified as belonging to ArOH or ArOD complexes. All of the bands were found to originate from the {sup 2}{Pi}{sub (3/2)}, {ital v}{double prime}=0 ground electronic state of the OH/OD radical. Two distinguishable vibronic structures were identified. A lower energy vibrational progression was assigned to the van der Waals stretch. This band system was designated as the {ital A}'' bands. A higher energy set of bands exhibited a different vibrational structure which did not fit a simple vibrational mode progression. These bands were labeled as the {ital U}'' system. Spectra showing partially resolved rotational structure were recorded for all of the observed ArOH/ArOD bands. The {ital A} and {ital U} systems were also distinguished by differences in their rotational structure and effects of H/D substitution on the vibrational and rotational parameters. Preliminary rotational analysis gave ground state constants ({ital B}{sup {double prime}}{sub 0}) of 0.100 cm{sup {minus}1} for ArOH and 0.098 cm{sup {minus}1} for ArOD. ({ital B}{sup {prime}}{sub {ital e}}) constants for the excited state of the {ital A} system were determined to be 0.178 cm{sup {minus}1} for ArOH and 0.168 cm{sup {minus}1} for ArOD. These rotational constants show that the Ar--OH/Ar--OD van der Waals bond has been considerably shortened upon electronic excitation.

• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6904063
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 92:2; 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
ADDUCTS
ARGON
ARGON COMPLEXES
COMPLEXES
ELECTRONIC STRUCTURE
ELEMENTS
EMISSION SPECTRA
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUIDS
FLUORESCENCE
GASES
HYDROXYL RADICALS
LUMINESCENCE
MOLECULAR STRUCTURE
NONMETALS
RADICALS
RARE GASES
ROTATIONAL STATES
SPECTRA
VIBRATIONAL STATES