Absorption and fluorescence of OClO Ã 2 A 2 -X̃ 2 B 1 in solid Ne, Ar, and Kr. I. Vibrationally unrelaxed Ã→X̃ emission

Chin Ping Liu*, Lih Huey Lai, Ying Yu Lee, Shao Ching Hung, Yuan-Pern Lee

*Corresponding author for this work

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

Dispersed laser-induced fluorescence of the à 2 A 2 →X̃ 2 B 1 transition of OClO in solid Ne in the spectral range 500-770 nm was recorded when the origin at 20991cm -1 was excited. Progressions with spacings near 939 and 446cm -1 are associated with vibrational modes ν 1 and ν 2 of the X̃ state. A simultaneous fit of both modes yields ω 1 =957.1±1.4, ω 2 =452.6±0.4, x 11 =4.47±0.04, x 22 =0.54±0.05, and x 12 =4.00±0.05cm -1 . When the 1 0 1 line of the Ã-X̃ system at 21699cm -1 was excited, vibrationally unrelaxed emission was observed in the spectral region 480-600 nm. Excitation of the 2 0 1 line at 21284cm -1 generated weak vibrationally unrelaxed progressions. The visible absorption spectrum of OClO in solid Ne in the region 415-488 nm was recorded with a Fourier-transform spectrometer, yielding ν 00 =20991.3, ν 1 =707.9, ν 2 =292.5, and 2ν 3 =887.6cm -1 for the à state. Simultaneous fits considering either only ν 1 and ν 2 modes or all three modes yield corresponding spectral parameters. Similar experiments were performed with OClO in solid Ar and Kr. Pronounced increases in ν 1 (716.0cm -1 in Ar and 712.5cm -1 in Kr) and ν 2 (302.3cm -1 in Ar and 303.0cm -1 in Kr) and a decrease in ν 00 (188cm -1 and 331cm -1 red-shifted, respectively) from that in the gas phase indicate substantial perturbation of the à state in solid Ar and Kr. An absorption continuum underlying the Ã-X̃ system is attributed to absorption to the 1̃ 2 A 1 state above the predissociation barrier. The phonon interaction increases and the threshold of the continuum decreases as the matrix host is altered from Ne to Ar to Kr.

Original languageEnglish
Pages (from-to)978-987
Number of pages10
JournalJournal of Chemical Physics
Volume109
Issue number3
DOIs
StatePublished - 1 Dec 1998

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