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使用连续波量子级联激光器测量 ν3 带中过氧羟自由基的吸收线强度。

Measurements of the absorption line strength of hydroperoxyl radical in the ν3 band using a continuous wave quantum cascade laser.

机构信息

Department of Chemical System Engineering, Graduate School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8656, Japan.

出版信息

J Phys Chem A. 2012 Jan 12;116(1):215-22. doi: 10.1021/jp207477n. Epub 2011 Dec 23.

Abstract

Mid-infrared absorption spectroscopy has been applied to the detection of the hydroperoxyl (HO(2)) radical in pulsed laser photolysis combined with a laser absorption kinetics reactor. Transitions of the ν(3) vibrational band assigned to the O-O stretch mode were probed with a thermoelectrically cooled, continuous wave mid-infrared distributed feedback quantum cascade laser (QCL). The HO(2) radicals were generated with the photolysis of Cl(2)/CH(3)OH/O(2) mixtures at 355 nm. The absorption cross section at each pressure was determined by three methods at 1065.203 cm(-1) for the F(1), 13(1,13) ← 14(1,14) transition in the ν(3) band. From these values, the absolute absorption cross section at zero pressure was estimated. The relative line strengths of other absorptions in the feasible emitting frequency range of the QCL from 1061.17 to 1065.28 cm(-1) were also measured, and agreed with values reproduced from the HITRAN database. The ν(3) band absorption strength was estimated from the analytically obtained absolute absorption cross section and the calculated relative intensity by spectrum simulation, to be 21.4 ± 4.2 km mol(-1), which shows an agreement with results of quantum chemical calculations.

摘要

中红外吸收光谱已应用于激光光解结合激光吸收动力学反应器中氢过氧自由基 (HO(2)) 的检测。通过使用热电冷却连续波中红外分布式反馈量子级联激光器 (QCL) 探测分配给 O-O 伸缩模式的 ν(3) 振动带的跃迁。HO(2)自由基通过 355nm 处的 Cl(2)/CH(3)OH/O(2)混合物的光解产生。在 1065.203cm(-1)处,在每个压力下通过三种方法确定 ν(3)带中的 F(1)、13(1,13) ← 14(1,14)跃迁的吸收截面。从这些值中,估计了零压力下的绝对吸收截面。还测量了 QCL 可行发射频率范围内(1061.17 至 1065.28cm(-1))其他吸收的相对谱线强度,与从 HITRAN 数据库重现的值一致。从分析获得的绝对吸收截面和通过光谱模拟计算的相对强度估计 ν(3)带吸收强度,为 21.4 ± 4.2km mol(-1),这与量子化学计算的结果一致。

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