Cryo-molecular spectroscopy and cryochemistry of unstable molecules--New application of the matrix isolation method

为了发展对基质中不稳定分子的光谱和低温化学研究，组装了用于辐照和光学及ESR测量的设施。使用内固定器械，获得了以下结果。(1)电离后，一些二硫杂环化合物、环丁烷和双环戊烷等张力烃以及三元醚的分子结构和电子态发生了显著的变化。理论分析一致地解释了观察到的变化。(2)波长依赖性的光化学变化被发现的几个不饱和烃，如二环戊二烯和环辛三烯。对反应机理进行了详细的讨论。(3)脂肪族羰基化合物和醚类自由基离子中质子的超精细耦合常数敏感地依赖于质子在自由基离子中的位置。对传统的估算耦合常数的方法进行了批判性的研究，目前正在进一步发展的实验技术包括LIF、PAS、X射线和激光共激发、高分辨ESR等。

In order to develop the spectroscopic and cryochemical study of unstable molecules in matrices facilities for irradiation and optical and ESR measurements were assembled. With the instrumentation the following findings were achieved.(1) Upon ionization remarkable changes of the molecular structure and electronic state were found for some dithia compounds, strained hydrocarbons such as cyclobutane and bicyclopentanes, and three-membered ethers. The observed changes were accounted for consistently by theoretical analyses.(2) Wavelength dependent photochemical changes were found for several unsaturated hydrocarbons such as dicyclopentadienes and cyclooctatriene. The reaction mechanism was discussed in detail.(3) The hyperfine coupling constant of protons in radical ions of aliphatic carbonyl compounds and ethers was found to depend sensitively upon the position of the proton in the radical ions. The conventional method to estimate the coupling constant was critically examined.Further experimental techniques involving LIF, PAS, jual excitation with X-rays and laser, high resolution ESR and so forth are now being developed.