ELECTRONIC SPECTRA AND RYDBERG STATES OF PERDEUTERO- AND PERHYDRO-METHYL CHLORIDES

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1974

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Ohio State University

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The electronic spectrum of $CD_{3}Cl$ has been recorded from 50 000 to 94 000 $cm^{-1}$; energies were determined to $\pm$ 20 $cm^{-1}$ and intensities to $\pm$ 15\%. The spectrum is similar in its general features to chat of $CH_{3}Cl$. In particular, two p-Rydberg series are easily discerned which lead to the components of the $^{2}E$ ground state of the $CD_{3}Cl^{+}$ ion, and which are analogous to those observed for $CH_{3}Cl$. The ionization potentials found are 90 730 and 91 350 $\pm$ 20 $cm^{-1}$; these are to be compared to 90 510 and 91 150 $cm^{-1}$ for $CH_{3}Cl$. The photoelectron spectrum of $CD_{3}Cl$ has also been $recorded^{1}$; here the lowest ionization potential, observed corresponds to the upper multiplet component of the $CD_{3}Cl^{+}$ ion. This is exactly analogous to what has been found by other workers for $CH_{3}Cl$. Detailed comparison of the spectra of $CD_{3}Cl$ and $CH_{3}Cl$ has made it possible to distinguish 0-0 Rydberg transitions from vibronic progressions in the complex region above 83 000 $cm^{-1}$. In this way many members of s-Rydberg series have been located and vibrational frequencies in the Rydber states have been determined. The vibronic structure in the lower Rydberg transitions will also be discussed.

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$^{1}$Acknowledgement is made to Norman A. Kuebler of Bell Laboratories for recording the photoelectron spectrum of $CD_{3}CI$.
Author Institution: Calspan Corporation; Department of Chemistry, North Texas State University; Department of Chemistry, California State University

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