3-甲基-2-丁烯-1-醇的光电离解离实验与理论研究  

Dissociative Photoionization of 3-methyl-2-buten-1-ol:Experiments and Calculations

作　　者：杨昊航 赵玉杰 YANG Haohang;ZHAO Yujie(School of Nuclear Science and Engineering,East China University of Technology,Nanchang 330013,China;Engineering Research Center of Nuclear Technology Application,East China Institute of Technology,Ministry of Education,Nanchang 330013,China)

机构地区：[1]东华理工大学核科学与工程学院,南昌330013 [2]东华理工大学核技术应用教育部工程研究中心,南昌330013

出　　处：《能源研究与管理》2022年第2期74-80,共7页Energy Research and Management

基　　金：国家自然科学基金(11275006);核技术应用教育部工程研究中心开放基金(HJSJYB2015-6)。

摘　　要：为探究新型燃料3-甲基-2-丁烯-1-醇的光化学性质,利用同步辐射真空紫外光结合超声膨胀分子束反射式飞行时间质谱研究3-甲基-2-丁烯-1-醇分子在8~12 eV光子能量范围内的光电离解离反应。通过测量母体分子的光电离质谱以及母体离子和主要碎片离子的光电离效率曲线,并使用Gaussian软件计算了电离解离过程中所有中间体、过渡态和产物的结构与能量,根据实验结果与理论计算,确定了3-甲基-2-丁烯-1-醇的电离能为8.69 eV,主要碎片离子C_(4)H_(7)O+和C_(5)H_(8)+的出现势分别为9.52和9.65 eV。提出了其可能的解离通道为C_(5)H_(10)O^(+)→C_(4)H_(7)O^(+)+CH_(3)与C_(5)H_(10)O^(+)→C_(5)H_(8)^(+)+H_(2)O,分析出解离机制主要为甲基自由基的脱离与H原子的转移,为3-甲基-2-丁烯-1-醇的大气光化学反应机制提供了参考。In order to explore the photochemical properties of the new fuel 3-methyl-2-buten-1-ol,the photoionization dissociation of 3-methyl-2-buten-1-ol molecule in the energy range of 8-12 eV was studied by synchrotron radiation vacuum ultraviolet(SR-VUV)light source and supersonic expanding molecular beam reflectron time-of-flight mass spectrometer system(TOF-MS).By measuring the photoionization mass spectra of the parent molecule and the photoionization efficiency curves of the parent molecule and major fragment ions.In addition,the structure and energy of all intermediates,transition states and products during ionization and dissociation were calculated using Gaussian software.Based on the experimental results and theoretical calculations,the ionization energy of 3-methyl-2-buten-1-ol molecule was determined to be 8.69 eV,and the appearance energies of the major fragment ions C_(4)H_(7)O^(+) and C_(5)H_(8)^(+)were 9.52 and 9.65 eV,respectively.The possible dissociation channels were proposed as C_(5)H_(10)O^(+)→C_(4)H_(7)O^(+)+CH_(3) and C_(5)H_(10)O^(+)→C_(5)H_(8)^(+)+H_(2)O.The dissociation mechanism was analyzed as mainly the detachment of methyl radicals and the transfer of H atoms,which provided a reference for the atmospheric photochemical reaction mechanism of 3-methyl-2-buten-1-ol.

关 键 词：3-甲基-2-丁烯-1-醇 光电离解离 同步辐射 量子化学计算 

分 类 号：TK16[动力工程及工程热物理—热能工程]