標題: 利用步進式掃描傅氏轉換時域解析紅外光譜法研究Criegee中間體(CH3)2COO之紅外吸收光譜
Infrared absorption spectra of Criegee intermediate (CH3)2COO detected with step-scan time-resolved Fourier-transform spectroscopy
作者: 王怡穎
李遠鵬
Wang, Yi-Ying
Lee, Yuan-Pern
應用化學系分子科學碩博士班
關鍵字: 大氣化學;氧化物;克里奇分子;紅外光譜;Criegee;infrared spectrum;radical;atmospheric chemistry
公開日期: 2017
摘要: Criegee intermediates are carbonyl oxides that play critical roles in the ozonolysis of alkenes in the atmosphere. So far, the infrared spectra of only the simplest Criegee intermediates CH2OO and CH3CHOO are reported. We report the transient infrared spectrum of the next member (CH3)2COO, produced from ultraviolet irradiation of a mixture of (CH3)2CI2 + O2 in a flow reactor and detected with a step-scan Fourier-transform spectrometer. The four observed bands provide definitive identification of (CH3)2COO. The observed vibrational wavenumbers and rotational contours agree with those predicted with quantum-chemical calculations. The rapid decay yields an estimate of the rate coefficient for self-reaction, ~1.610−10 cm3 molecule−1 s−1. The direct IR detection of (CH3)2COO should prove useful for field measurements and laboratory investigations of related Criegee mechanism.
Criegee intermediates are carbonyl oxides that play critical roles in the ozonolysis of alkenes in the atmosphere. So far, the infrared spectra of only the simplest Criegee intermediates CH2OO and CH3CHOO are reported. We report the transient infrared spectrum of the next member (CH3)2COO, produced from ultraviolet irradiation of a mixture of (CH3)2CI2 + O2 in a flow reactor and detected with a step-scan Fourier-transform spectrometer. The four observed bands provide definitive identification of (CH3)2COO. The observed vibrational wavenumbers and rotational contours agree with those predicted with quantum-chemical calculations. The rapid decay yields an estimate of the rate coefficient for self-reaction, ~1.610−10 cm3 molecule−1 s−1. The direct IR detection of (CH3)2COO should prove useful for field measurements and laboratory investigations of related Criegee mechanism.
URI: http://etd.lib.nctu.edu.tw/cdrfb3/record/nctu/#GT070352415
http://hdl.handle.net/11536/140464
Appears in Collections:Thesis