Spectroscopic detection and characterization of the FS[sub 2] free radical

Journal Article · Sun May 01 00:00:00 EDT 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.467074· OSTI ID:5120504

Zhuo, Q; Karolczak, J; Clouthier, D J ^[1]

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1. Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States)

An extensive vibronic band system of the FS[sub 2] radical in the 700--485 nm region has been observed for the first time by laser-induced fluorescence (LIF) probing of the products of the reaction of F[sub 2] with various sulfur-containing compounds. Jet-cooled spectra were obtained by reacting fluorine with COS, H[sub 2]S, or CS[sub 2] in the body of a continuous supersonic jet, just prior to expansion. Vibrational analysis of the jet spectra gives [nu][sub 1][sup [prime]] = 768, [nu][sub 2][sup [prime]] = 217, [nu][sub 3][sup [prime]] = 495, [nu][sub 1][sup [double prime]] = 705, [nu][sub 2][sup [double prime]] = 293, [nu][sub 3][sup [double prime]] = 684, and [ital T][sub 00]=14 922 cm[sup [minus]1], all in good agreement with [ital ab] [ital initio] predictions for the FS[sub 2] free radical. A rotational analysis of the high-resolution spectrum of the 3[sup 5][sub 0] band shows that the transition is polarized out-of-plane, with spin splittings characteristic of a molecule with a single unpaired electron. The rotational constants and spin--rotation interaction constants were determined with good precision for the ground and excited states. By combining the rotational constants with our [ital ab] [ital initio] estimates of the S--F bond length, the following structural parameters were obtained: [ital r](S--F)=1.651 A, [ital r](S--S)=1.865(5) A, and [theta](FSS)=109.1(1)[degree] for the [ital [tilde X]] [sup 2][ital A][double prime] state and [ital r](S--F)=1.642 A, [ital r](S--S)=2.105(5) A, and [theta](FSS)=97.6(1)[degree] for the [ital [tilde A]] [sup 2][ital A][prime] state.

• DOE Contract Number: FG05-86ER13544
• OSTI ID: 5120504
• Journal Information: Journal of Chemical Physics; (United States), Vol. 100:9; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
SULFUR FLUORIDES
LASER SPECTROSCOPY
CHEMICAL REACTIONS
COOLING
EXCITED STATES
FLUORESCENCE
GROUND STATES
JETS
RADICALS
ROTATIONAL STATES
VIBRATIONAL STATES
YIELDS
ENERGY LEVELS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
LUMINESCENCE
SPECTROSCOPY
SULFUR COMPOUNDS
664200* - Spectra of Atoms & Molecules & their Interactions with Photons- (1992-)
664100 - Theory of Electronic Structure of Atoms & Molecules- (1992-)