標題: Infrared absorption of gaseous CH(3)OO detected with a step-scan Fourier-transform spectrometer
作者: Huang, Deng-Ruei
Chu, Li-Kang
Lee, Yuan-Pern
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 21-十二月-2007
摘要: CH(3)OO radicals were produced upon irradiation of a flowing mixture of CH(3)I and O(2) with a KrF excimer laser at 248 nm. A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to record temporally resolved IR absorption spectra of reaction intermediates. Transient absorption bands with origins at 3033, 2954, 1453, 1408, 1183, 1117, 3020, and 1441 cm(-1) are assigned to nu(1)-nu(6), nu(9), and nu(10) modes of CH(3)OO, respectively, close to wavenumbers reported for CH(3)OO isolated in solid Ar. Calculations with density-functional theory (B3LYP/aug-cc-pVTZ) predicted the geometry and the vibrational wavenumbers of CH(3)OO; the vibrational wavenumbers and relative IR intensities of CH(3)OO agree satisfactorily with these observed features. The rotational contours of IR spectra of CH(3)OO, simulated based on ratios of predicted rotational parameters for the upper and lower states and on experimental rotational parameters of the ground state, agree satisfactorily with experimental results; the mixing ratios of a-, b-, and c-types of rotational structures were evaluated based on the direction of dipole derivatives predicted quantum chemically. A feature at 995 cm(-1), ascribed to CH(3)OOI from a secondary reaction of CH(3)OO with I, was also observed. (c) 2007 American Institute of Physics.
URI: http://dx.doi.org/10.1063/1.2807241
http://hdl.handle.net/11536/10000
ISSN: 0021-9606
DOI: 10.1063/1.2807241
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 127
Issue: 23
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