Photodissociation of the Fluorene Cation: A Fourier Transform Ion Cyclotron Resonance Mass Spectrometric Study
Photodissociation of the Fluorene Cation: A Fourier Transform Ion Cyclotron Resonance Mass Spectrometric Study
复制标题
芴阳离子的光解：傅里叶变换离子回旋共振质谱研究
DOI：
10.1021/jp0100708
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发表时间：
2001
影响因子：
2.9
通讯作者：
M. Vala
中科院分区：
文献类型：
--
作者：
M. Dibben;D. Kage;J. Szczepanski;J. Eyler;M. Vala
用傅里叶变换离子回旋共振(ICR)质谱仪研究了气相荧阳离子的光解过程。宽带可见光和紫外光照射时间相对较短(∼为0.5，S)，主要导致氢原子顺序损失，损失1~5个氢原子。对于几个前体离子来说，一个相对较小的分解途径是失去H2(或2H原子)。较长的辐照时间会导致多个C-−-C键断裂产生不同的产物。M/z166→过程的“作用”谱显示了两个主要的电子吸收带，这两个带与母离子先前的基质吸收谱很好地关联。在ICR质谱计中分离出C13H+10-n(n=0−5)物种，经进一步辐照后，其光解动力学进行了研究。通过求解控制动力学的适当的耦合微分方程式，使之能够与实验数据进行拟合。反应速率常数和分枝比。
The photodecomposition of the vapor phase fluorene cation has been studied using Fourier transform ion cyclotron resonance (ICR) mass spectrometry. Broad-band visible and ultraviolet irradiation for relatively short times (∼0.5 s) is shown to lead predominantly to sequential hydrogen atom loss, with one to five hydrogens lost. A relatively minor decomposition route for several precursor ions is the loss of H2 (or 2H atoms). Longer irradiation times lead to various products resulting from multiple C−C bond cleavages. The “action” spectrum for the m/z 166 → 165 process reveals two major electronic absorption bands which correlate well with a previous matrix absorption spectrum of the parent ion. The C13H+10-n (n = 0−5) species have been isolated in the ICR mass spectrometer, irradiated further, and their photodecomposition followed kinetically. Solution of the appropriate coupled differential equations that govern the kinetics has enabled fits to the experimental data. Rate constants and branching ratios fo...