Formation of H3O+ from alcohols and ethers induced by intense laser fields.
Formation of H3O+ from alcohols and ethers induced by intense laser fields.
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DOI：
10.1002/rcm.4438
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发表时间：
2010-03
期刊：
影响因子：
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通讯作者：
Tatsuro Shirota;Narutoshi Mano;M. Tsuge;K. Hoshina
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文献类型：
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作者：
Tatsuro Shirota;Narutoshi Mano;M. Tsuge;K. Hoshina
通过飞行时间质谱（TOF MS）研究了强激光场（800 nm，100 fs，约1 x 10（14）W/cm）作用下醇类（乙醇、2-丙醇、1-丙醇、2-丁醇）和醚类（乙醚和乙基甲基醚）及其氘代物种生成H（3）O（+）的过程。除乙基甲基醚外，所有这些化合物都有H（3）O（+）生成。H（（3-n））D（n）O（+）（n = 0，1，2，3）的飞行时间信号随飞行时间的增加而扩展，通过对信号的分析，证实了反应是通过从中间产物C（2）H（（5-m））D（m）O（+）（m = 0-5）的亚稳态解离进行的. H（（3-n））D（n）O（+）信号分布的共同形状包含时间常数的两个主要分布，即，分别为<50 ns和大约500 ns的快分量和慢分量。H（（3-n））D（n）O（+）的分支比被解释为C（2）H（4）-OH（+）中C-C位上的四个氢原子完全乱序的结果，并且在H（（3-n））D（n）O（+）产生之前的1 ns内，OH基团中的一个氢原子与其他四个氢原子部分交换（18-38%）。对C（2）H（5）O（+）的异构体和过渡态进行了从头计算，并对H（3-n）D（n）O（+）的生成机理进行了讨论.此外，还发现了一种具有复杂结构和两条异构化途径的稳定异构体参与了H（3）O（+）的形成过程。
The processes of H(3)O(+) production from alcohols (ethanol, 2-propanol, 1-propanol, 2-butanol) and ethers (diethyl ether and ethyl methyl ether), and their deuterium-substituted species, by intense laser fields (800 nm, 100 fs, approximately 1 x 10(14) W/cm) were investigated through time-of-flight (TOF) mass spectrometry. H(3)O(+) formation was observed for all these compounds except for ethyl methyl ether. From the analysis of TOF signals of H((3-n))D(n)O(+) (n = 0, 1, 2, and 3) that have expanding tails with increasing flight time, it has been confirmed that the reaction proceeds through metastable dissociation from the intermediate species C(2)H((5-m))D(m)O(+)(m = 0-5). The common shape of the H((3-n))D(n)O(+) signal profiles contains two major distributions in the time constant, i.e., fast and slow components of <50 ns and approximately 500 ns, respectively. The H((3-n))D(n)O(+) branching ratio is interpreted to be the result of complete scrambling of four hydrogen atoms at the C-C site in C(2)H(4)-OH(+), and partial exchange (18-38%) of a hydrogen atom in the OH group with four other hydrogen atoms within 1 ns prior to H((3-n))D(n)O(+) production. Ab initio calculations for the isomers and transition states of C(2)H(5)O(+) were also performed, and the observed H((3-n))D(n)O(+) production mechanism has been discussed. In addition, a stable isomer having a complex structure and two isomerization pathways were discovered to contribute to the H(3)O(+) formation process.