ROVIBRONIC INTERACTIONS AND l-UNCOUPLING IN THE HIGH-RYDBERG STATES OF HCO CONVERGING TO THE (010) STATE OF THE CATION
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Date
2000
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Ohio State University
Abstract
We report the ionization-detected absorption spectra of vibrationally autoionizing Rydberg states converging to the (010) level of $HCO^{+}$. Resonances are isolated by transitions from photoselected rotational levels in the $\Sigma^{+}$ and $\Sigma^{-}$ Renner-Teller components of the (010) band of the $3p\pi^{2}\Pi$ Rydberg state. We systematically compare spectra in order to characterize observed resonances in terms of the good total angular momentum quantum number, $N$. Rydberg analysis establishes the convergence of series to detailed cation-care rotational quantum numbers, $N^{+}$. Interactions between Rydberg orbital and core rotational angular momentum are found to conform with a coupling intermediate between Hund's cases (b) and (d). Splitting patterns further assign certain features according to predominant case (b) composition.
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Author Institution: Department of Chemistry, Purdue University