CHARACTERIZATION OF THE $\tilde{X}{^{2}}A_{1} (0,0,0)$ GROUND VIBRONIC STATE OF $CH^{+}_{2}$ BY PFI-ZEKE PHOTOELECTRON SPECTROSCOPY

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2002

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Ohio State University

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The $\tilde{X} ^{2}A_{1} (0,0,0)$ ground vibronic state of $CH^{+}_{2}$ has been studied by pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy by recording transitions from the $\tilde{X} {^{3}}B_{1} (0,0,0)$ ground vibronic state of $CH_{2}$ which has been produced by photolysis of $CH_{2}CO$ at 351 nm. The rotational energy level structure and the spin-rotation splittings of levels with $K_{a} \geq 1$ could be resolved. The rotational structure in the $\tilde{X} {^{2}}A_{1} (0,0,0)$ state deviates strongly from that of a rigid rotor. The adiabatic ionization potential of ${^{3}}CH_{2}$ has been determined to be $(83772\pm 3) cm^{-1}$. Analysis of the photoionization selection rules indicates that the photoelectron is ejected as a superposition of $\ell$ even and $\ell$ odd partial waves.

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Author Institution: Physical Chemistry

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