巴豆酸甲酯的光电离实验与理论研究

doi:10.7523/j.issn.2095-6134.2021.02.007

中国科学院大学学报 ›› 2021, Vol. 38 ›› Issue (2): 207-216.DOI: 10.7523/j.issn.2095-6134.2021.02.007

巴豆酸甲酯的光电离实验与理论研究

孙瑞瑞¹, 李淹博², 陈军², 孟庆慧², 王欢欢², 张航², 单晓斌², 刘付轶², 盛六四²

1. 中国科学技术大学物理学院, 合肥 230026;
2. 中国科学技术大学国家同步辐射实验室, 合肥 230029

收稿日期:2019-03-29 修回日期:2019-05-21 发布日期:2021-03-15
通讯作者: 李淹博
基金资助:
Supported by the National Natural Science Foundation of China (11575178,41575126)

Dissociative photoionization of methyl crotonate: experimental and theoretical insights

SUN Ruirui¹, LI Yanbo², CHEN Jun², MENG Qinghui², WANG Huanhuan², ZHANG Hang², SHAN Xiaobin², LIU Fuyi², SHENG Liusi²

1. School of Physical Sciences, University of Science and Technology of China, Hefei 230026, China;
2. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China

Received:2019-03-29 Revised:2019-05-21 Published:2021-03-15
Supported by:
Supported by the National Natural Science Foundation of China (11575178,41575126)

摘要/Abstract

摘要： 利用可调谐同步辐射与飞行时间质谱实验，研究巴豆酸甲酯在9.0~14.5 eV能量范围内的真空紫外光电离和光解离过程。通过光电离效率曲线测定巴豆酸甲酯的电离能以及主要碎片离子C₄H₅O₂⁺、C₄H₅O⁺、C₄H₄O⁺、C₂H₃O₂⁺、C₃H₅⁺和C₂H₅⁺的出现势，分别为10.11、10.73、10.88、12.2、11.93（12.77）和12.44 eV。通过实验结果和G3B3计算结果的比较，分析主要碎片C₄H₅O₂⁺+CH₃、C₄H₅O⁺+CH₃O、C₄H₄O⁺+CH₄O、C₂H₃O₂⁺+C₃H₅、C₃H₅⁺+C₂H₃O₂（CO+CH₃O）和C₂H₅⁺+C₃H₃O₂的可能解离通道以及解离通道上经历的过渡态和中间体。在巴豆酸甲酯的光电离和光解离过程中，大多数碎片是母体离子异构化之后形成的，氢转移和开闭环是主要的过程。

关键词: 巴豆酸甲酯, 同步辐射, 质谱法, 光解离, G3B3计算

Abstract: The photoionization and dissociation of methyl crotonate have been studied by tunable vacuum ultraviolet synchrotron radiation coupled with time-of-flight mass spectrometer in the photon energy region 9.0-14.5 eV. The ionization energy of methyl crotonate and the appearance energies for major fragments C₄H₅O₂⁺, C₄H₅O⁺,C₄H₄O⁺, C₂H₃O₂⁺, C₃H₅⁺, and C₂H₅⁺ are determined to be 10.11, 10.73, 10.88, 12.2, 11.93(12.77), and 12.44 eV, respectively, according to the photoionization efficiency curves. Based on the experimental AEs and energies predicted by ab initio G3B3 calculations, possible formation channels for the major fragments C₄H₅O₂⁺+CH₃, C₄H₅O⁺+CH₃O, C₄H₄O⁺+CH₄O, C₂H₃O₂⁺+C₃H₅, C₃H₅⁺+C₂H₃O₂(CO+CH₃O), and C₂H₅⁺+C₃H₃O₂ are proposed. Transition states and intermediates involved in the dissociation channels are also located. The majority of the proposed channels occur through isomerization processes prior to dissociations. Hydrogen shift and ring closing/opening are found to be the dominant processes during photoionization and dissociation of methyl crotonate.

Key words: methyl crotonate, synchrotron radiation, mass spectrometry, dissociative photoionization, G3B3 calculations

中图分类号:

O641

孙瑞瑞, 李淹博, 陈军, 孟庆慧, 王欢欢, 张航, 单晓斌, 刘付轶, 盛六四. 巴豆酸甲酯的光电离实验与理论研究[J]. 中国科学院大学学报, 2021, 38(2): 207-216.

SUN Ruirui, LI Yanbo, CHEN Jun, MENG Qinghui, WANG Huanhuan, ZHANG Hang, SHAN Xiaobin, LIU Fuyi, SHENG Liusi. Dissociative photoionization of methyl crotonate: experimental and theoretical insights[J]. Journal of University of Chinese Academy of Sciences, 2021, 38(2): 207-216.

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巴豆酸甲酯的光电离实验与理论研究

Dissociative photoionization of methyl crotonate: experimental and theoretical insights

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