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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dispersed Fluorescence Spectroscopy of Jet-Cooled Isobutoxy and 2-Methyl-1-butoxy Radicals
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Dispersed Fluorescence Spectroscopy of Jet-Cooled Isobutoxy and 2-Methyl-1-butoxy Radicals

机译：射流冷却的异丁氧基和2-甲基-1-丁氧基自由基的分散荧光光谱

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摘要

We report dispersed fluorescence (DF) spectra of the iso-butoxy and 2-methyl-1-butoxy radicals produced by photolysis of corresponding nitrites in supersonic jet expansion. Different vibrational structures have been observed in the DF spectra when different vibronic bands in the laser-induced fluorescence (LW) spectra of each radical Were pumped, which suggests that those vibronic bands be assigned to different conformers. Spectra simulated using calculated vibrational frequencies and Franck Condon factors well reproduce the experimentally observed ones and support the assignment of the vibronic bands in the LIF spectra to the two lowest-energy conformers of each radical. DF spectra obtained by pumping the (B) over tilde <- (X) over tilde origin bands of the LIT spectra are dominated by CO stretch progresSions because of the large difference in CO bond length between the ground ((X) over tilde) and the second excited ((X) over tilde) electronic states. Furthermore, with non-CO stretch-bands pumped, the DF spectra are dominated by progressions of combination bands, of the CO stretch and the pumped modes as a result of Duschinsky mixing. (A) over tilde-(X) over tilde separation of both conformers of the isobutoxy radical has also been determined in the experiment.
机译：我们报告了由超音速射流膨胀中相应的亚硝酸盐的光解产生的异丁氧基和2-甲基-1-丁氧基的分散荧光（DF）光谱。当泵送每个自由基的激光诱导荧光（LW）光谱中的不同振动带时，在DF光谱中观察到了不同的振动结构，这表明这些振动带被分配给不同的构象体。使用计算的振动频率和弗朗克·康登因子模拟的光谱很好地再现了实验观察到的光谱，并支持将LIF光谱中的振动带分配给每个自由基的两个最低能量构象体。通过将波浪线（B）泵到LIT谱线的波浪线起源带上而获得的DF谱由CO拉伸过程支配，这是因为地面（波浪线上的（X））与波浪线之间的CO键长差异很大。第二个激发（在波浪号上的（X））电子态。此外，在泵送非CO拉伸带的情况下，由于Duschinsky混合，DF谱由组合带，CO拉伸和泵浦模式的进行控制。在实验中还确定了（A）超过代字号-（X）超过了代字号的异丁氧基的两个构象体的分离。

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