VACUUM ULTRAVIOLET CIRCULAR DICHROISM SPECTRUM OF (+)-3-METHYLCYCLOPENTANONE USING SYNCHROTRON $RADIATION^{\ast}$

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1982

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Ohio State University

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This study reports vacuum ultraviolet circular dichroism (CD) measurements on (+)-3-methylcyclopentenanone vapor using synchrotron radiation as a light source.1 The spectrum will be presented from 2050A to 1325A. The valence shell spectra of ketones are poorly understood. The first three regions of intense CD occur at 3030A, 1960A and 1666A. only the assignment of the nπ transition which falls in the 3030A-2780A region, is not questioned. The 1960A region has been previously assigned as nσ,σπ,n2π,ππ and n−3s (Rydberg)2. Recent results from electrochromism, showed the electronic transition moment for this transition to be consistent with an nG or n−3s assignment. Based on polarizability results the electrochromism studies favored the n−3s assignment. However, there are indications that there may be two transitions in this region. The third region of intense CD at 1666A has been assigned as n=d(Rydberg) and ππ,2 We calculate theoretical rotational strenghts and compare them to experimental values. The results are used to further understand the spectra of ketones. The results indicate that the circular dichroism of the 1960A bond arises from the no transition and that an assignment of ππ is consistent with the circular dichroim at 1666A. In addition, the results indicate which polarizabilities should be used in rotational strength calculations.

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This work was supported by the National Science Foundation (Grant CHE=8108534) and the Research Corporation. 1Measurements were carried out at the Synchrotron Radiation Center, University of Wiaconsin-Madison. 2M.B. Robin Higher Excited States of Polatomic Molecules Vol. II, Academic Press, 1975. 3C.C. Causley and B.R. Russell, J. Chem. Phys. 68, 3797 (1978).

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