MONOENERGETIC PHOTOLYTIC REACTIONS.
Final rept., 1 Oct 61-1 Oct 65,
NORTHWESTERN UNIV EVANSTON ILL
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The photolysis of cyclobutanone was investigated. Some work on the mechanism confirmed that it was a simple photolytic decomposition. One of the directly formed products is cyclopropane. Since the light quantum excites cyclobutanone with about 112 kcalmole, the initially formed cyclopropane will similarly be highly excited. In fact the energy of the cyclopropane can be varied continuously since the wavelength irradiating the cyclobutanone can be varied continuously. A vibrationally excited molecule is thus had whose decomposition can be studied as the excitation energy is varied. Such systems are needed as test cases in the theory of reaction rates. Much time was spent developing an adequate theory for these reactions. A new way of analysing rate equations was proposed, for molecular systems that undergo reactions from many quantum levels. Some work in the vacuum ultraviolet region was also done. A high intensity light source was developed for use in this region, operated by microwaves at high power. With this source and a monochromator, thresholds for ionization of inorganic molecules were measured. Investigations relevant to the theory of absolute reaction rates were also performed. Author
- Radiation and Nuclear Chemistry