A new approach toward transition state spectroscopy.
A new approach toward transition state spectroscopy.
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过渡态光谱学的新方法。
DOI：
10.1039/c3fd20160k
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发表时间：
2013
影响因子：
3.4
通讯作者：
R. Field
中科院分区：
文献类型：
--
作者：
Kirill Prozument;R. G. Shaver;Monika A. Ciuba;J. Muenter;G. B. Park;J. Stanton;Hua Guo;Bryan M. Wong;D. S. Perry;R. Field
啁啾脉冲毫米波（CPmmW）转动光谱提供了一类关于光解过渡态的新信息。在转动光谱测量强度确定物种异构体振动人口，提供的旋转人口可以热化。讨论了在低和高初始转动激发极限下S（0）偏乙烯基的形成和检测。CPmmW光谱的193 nm光解的乙烯基氰（丙烯腈）包含J = 0-1跃迁的HCN和HNC的20多个振动能级，但没有过渡的乙烯基或高激发本地弯曲振动水平的乙炔。未观察到HCN的亚乙烯基副产物的原因进行了讨论。
Chirped-Pulse millimetre-Wave (CPmmW) rotational spectroscopy provides a new class of information about photolysis transition state(s). Measured intensities in rotational spectra determine species-isomer-vibrational populations, provided that the rotational populations can be thermalized. The formation and detection of S(0) vinylidene is discussed in the limits of low and high initial rotational excitation. CPmmW spectra of 193 nm photolysis of vinyl cyanide (acrylonitrile) contain J = 0-1 transitions in more than 20 vibrational levels of HCN and HNC, but no transitions in vinylidene or highly excited local-bender vibrational levels of acetylene. Reasons for the non-observation of the vinylidene co-product of HCN are discussed.