Rajakumar B, Flad Jonathan E, Gierczak Tomasz, Ravishankara A R, Burkholder James B
Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, Colorado 80305-3328, USA.
J Phys Chem A. 2007 Sep 20;111(37):8950-8. doi: 10.1021/jp073339h. Epub 2007 Aug 18.
The visible absorption spectrum of the acetyl radical, CH(3)CO, was measured between 490 and 660 nm at 298 K using cavity ring-down spectroscopy. Gas-phase CH(3)CO radicals were produced using several methods including: (1) 248 nm pulsed laser photolysis of acetone (CH(3)C(O)CH(3)), methyl ethyl ketone (MEK, CH(3)C(O)CH(2)CH(3)), and biacetyl (CH(3)C(O)C(O)CH(3)), (2) Cl + CH(3)C(O)H --> CH(3)C(O) + HCl with Cl atoms produced via pulsed laser photolysis or in a discharge flow tube, and (3) OH + CH(3)C(O)H --> CH(3)CO + H(2)O with two different pulsed laser photolysis sources of OH radicals. The CH(3)CO absorption spectrum was assigned on the basis of the consistency of the spectra obtained from the different CH(3)CO sources and agreement of the measured rate coefficients for the reaction of the absorbing species with O(2) and O(3) with literature values for the CH(3)CO + O(2) + M and CH(3)CO + O(3) reactions. The CH(3)CO absorption spectrum between 490 and 660 nm has a broad peak centered near 535 nm and shows no discernible structure. The absorption cross section of CH(3)CO at 532 nm was measured to be (1.1 +/- 0.2) x 10(-19) cm(2) molecule(-1) (base e).
在298 K下,使用光腔衰荡光谱法测量了乙酰基(CH(3)CO)在490至660 nm之间的可见吸收光谱。通过多种方法产生气相CH(3)CO自由基,包括:(1)用248 nm脉冲激光光解丙酮(CH(3)C(O)CH(3))、甲乙酮(MEK,CH(3)C(O)CH(2)CH(3))和丁二酮(CH(3)C(O)C(O)CH(3));(2)通过脉冲激光光解或在放电流管中产生的Cl原子与CH(3)C(O)H反应生成CH(3)C(O)+HCl;(3)用两种不同的OH自由基脉冲激光光解源使OH与CH(3)C(O)H反应生成CH(3)CO+H(2)O。基于从不同CH(3)CO源获得的光谱的一致性以及所测量的吸收物种与O(2)和O(3)反应的速率系数与CH(3)CO+O(2)+M和CH(3)CO+O(3)反应的文献值的一致性,确定了CH(3)CO吸收光谱。490至660 nm之间的CH(3)CO吸收光谱有一个以535 nm附近为中心的宽峰,且无明显结构。测量得到CH(3)CO在532 nm处的吸收截面为(1.1±0.2)×10(-19) cm(2) molecule(-1)(自然底数e)。