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

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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.