Flash pyrolysis vacuum ultraviolet photoionization mass spectrometry of cycloheptane: A study of the initial decomposition mechanism
Flash pyrolysis vacuum ultraviolet photoionization mass spectrometry of cycloheptane: A study of the initial decomposition mechanism
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DOI：
10.1177/14690667221142699
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发表时间：
2022-12
影响因子：
1.3
通讯作者：
Kuanliang Shao;Ge Sun;Mariah Gomez;Xinghua Liu;Jingsong Zhang
中科院分区：
文献类型：
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作者：
Kuanliang Shao;Ge Sun;Mariah Gomez;Xinghua Liu;Jingsong Zhang
采用闪速裂解-真空紫外（118.2nm）单光子电离飞行时间质谱联用技术研究了环庚烷在295 ~ 1380 K温度范围内的热分解。环庚烷的C-C键断裂导致1，7-庚基双自由基被认为是引发步骤。1，7-庚基双自由基可以很容易地异构化为1-庚烯并分解成几个片段，解离为·C4 H9和·C3 H5是主要的产物通道。1，7-庚基双自由基可以进行直接解离，如C5 H10物质的产生所证明的。在UCCSD（T）/cc-pVDZ//UB 3LYP/cc-pVDZ理论水平上对环庚烷的初始反应路径进行了量子化学计算.其他可能的引发通道，以及一些次级反应产物，也被确定。
Thermal decomposition of cycloheptane was studied using flash pyrolysis coupled with vacuum ultraviolet (118.2 nm) single photon ionization time-of-flight mass spectrometry at temperatures ranging from 295 K to 1380 K. C-C bond breaking of cycloheptane leading to the 1,7-heptyl diradical was considered as the initiation step. The 1,7-heptyl diradical could readily isomerize to 1-heptene and decompose into several fragments, with dissociation to •C4H9 and •C3H5 as the predominant product channel. The 1,7-heptyl diradical could undergo direct dissociation, as evidenced by the production of the C5H10 species. Quantum chemistry calculations at UCCSD(T)/cc-pVDZ//UB3LYP/cc-pVDZ level of theory on the initial reaction pathways of cycloheptane were also carried out to support the experimental observations. Other possible initiation channels, as well as some secondary reaction products, were also identified.