ZERO ELECTRON KINETIC ENERGY PULSED FIELD IONIZATION (ZEKE) SPECTROSCOPY OF $CdCH_{3}$ AND
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Date
1997
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Ohio State University
Abstract
The two-color (1+1)REMPI and ZEKE spectra of the $CdCH_{3}$ and $ZnCH_{3}$ radicals are reported for the first time. Based upon the observed intensities in the ZEKE spectrum for $CdCH_{3}$, via traditions to different vibrational levels of the $\tilde{A}^{2}E$ intermediate state, the bund previously assigned as the upper spin-orbit component of the vibrationless level of the $\tilde{A}^{2}E \leftarrow \tilde{X}^{2}A_{1}$ transition in neutral $CdCH_{3}$ is reassigned. This band which has now been observed in both LIF and REMPI experiments, is reassigned as the $6^{1}_{0}$ band of the lower spin-orbit component, $^{2}E_{1/2}$. The ZEKE spectra, taken via various intermediate rovibronic levels, are used to reveal rovibrational structure of the $CdCH_{3}$ and $ZnCH_{3}$ cations and to measure the adiabatic ionization energies for both radicals. These radicals belong to the $C_{3}$, point group and are therefore subject to a Jahn-Teller interaction in the $\tilde{A}$ state, which allows a broader range of {K^{\prime}} states to be accessible in the LIF and REMPI experiments thereby enabling access to a broader range of K states for the ions in the ZEKE experiment. The resolved K structure in the level with one quanta of $\nu_{6}$ excitation in the ion enables estimates of both the rotational constant A and the coriolis coupling constant $\sigma \zeta_{1}$ to be made. Vibrational frequencies and assignments for the ions will be reported.
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Author Institution: Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University