Lee Gi Woo, Lee Sang Kuk
Department of Chemistry and The Chemistry Institute for Functional Materials, Pusan National University, Pusan 609-735, Republic of Korea.
J Phys Chem A. 2006 Feb 9;110(5):1812-6. doi: 10.1021/jp0557316.
A precursor, 1,2,4-trimethylbenzene, seeded in a large amount of an inert carrier gas, helium, was electrically discharged in a corona-excited supersonic expansion using a pinhole-type glass nozzle. The blue-green colored fluorescence emanating from the downstream jet was recorded with a long path monochromator to observe the vibronic emission spectrum of the benzyl-type radical formed. Analysis of the spectrum suggests that the most dominant product of the corona discharge is the 3,4-dimethylbenzyl radical formed by extracting a hydrogen atom from the methyl group at the 4-position. The electronic energies of the D1 and D2 states and the vibrational mode frequencies of the 3,4-dimethylbenzyl radical were accurately obtained for the first time by comparison with those from an ab initio calculation as well as those of the known vibrational mode frequencies of the precursor.
前驱体1,2,4-三甲基苯被注入大量惰性载气氦气中,通过针孔型玻璃喷嘴在电晕激发的超声速膨胀中进行放电。用长路径单色仪记录下游射流发出的蓝绿色荧光,以观察所形成的苄基型自由基的振动发射光谱。光谱分析表明,电晕放电的最主要产物是通过从4位甲基上提取一个氢原子而形成的3,4-二甲基苄基自由基。通过与从头算计算结果以及前驱体已知振动模式频率进行比较,首次精确获得了3,4-二甲基苄基自由基D1和D2态的电子能量以及振动模式频率。