Cavity Ring-Down Spectroscopy of the Benzyl Radical
Cavity Ring-Down Spectroscopy of the Benzyl Radical
复制标题
苄基自由基的光腔衰荡光谱
DOI：
10.1021/jp027280k
复制
发表时间：
2003
影响因子：
2.9
通讯作者：
M. Koshi
中科院分区：
文献类型：
--
作者：
Kenichi Tonokura and;M. Koshi
在298 K、20 Torr的氩气或氮气稀释液中，利用光腔衰荡光谱（CRDS）测量了苄基自由基（C6 H5 CH 2·）在450 nm附近振动混合12 A2 − 22 B1激发态区域的电子吸收光谱。吸收截面由CRDS吸收和自由基-自由基交叉反应的速率确定。在447.7nm处，σ苄基=（2.2 ± 0.8）× 10-18 cm ~ 2分子~（-1）（碱e）。在模拟过程中得到了苄基自由基与Cl原子反应的速率常数：k（C6 H5 CH 2 + Cl）=（2.5 ± 1.0）× 10-10 cm 3 molecule-1 s-1.含时密度泛函理论计算支持的解释的吸收光谱的苄基自由基。
The electronic absorption spectrum of the benzyl radical (C6H5CH2•) has been measured in the region of the vibrationally mixed 12A2−22B1 excited states near 450 nm by cavity ring-down spectroscopy (CRDS) in 20 Torr of argon or nitrogen diluents at 298 K. The absorption cross section was determined from the CRDS absorption and the rates of radical−radical cross reactions. At 447.7 nm, σbenzyl = (2.2 ± 0.8) × 10-18 cm2 molecule-1 (base e). The rate constant for the reaction of benzyl radicals with Cl atoms was derived during the modeling: k(C6H5CH2 + Cl) = (2.5 ± 1.0) × 10-10 cm3 molecule-1 s-1. Time-dependent density functional theory calculations support the interpretation of the absorption spectrum of the benzyl radical.