一种新的过渡态光谱方法
A New Approach toward Transition State Spectroscopy
摘要：
啁啾脉冲毫米波（CPmmW）转动光谱提供了一类新的关于光解过渡态的信息。在转动光谱测量强度确定物种异构体振动人口，只要转动人口可以热化。讨论了在低和高初始转动激发极限下S 0偏乙烯的形成和检测。丙烯腈193 nm光解的CPmmW谱中，HCN、HNC的20多个振动能级有J=0-1跃迁，而乙炔的亚乙烯基或高激发局域弯曲振动能级没有J = 0 - 1跃迁.未观察到HCN的亚乙烯基副产物的原因进行了讨论。
英文摘要：
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 rotational populations can be thermalized. The formation and detection of S0 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, 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.
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