AN EXPERIMENTAL DETERMINATION OF ANHARMONIC TERMS IN THE VIBRATIONAL HAMILTONIAN OF $HCO^{+}$.
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Date
1999
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Ohio State University
Abstract
We report a harmonic frequency $\omega_{2} = 842.464 cm^{-1}$, an anharmonic constant, $x_{22} = -3.15 cm^{-1}$ and a vibrational angular momentum splitting constant $g_{22} = 3.22 cm^{-1}$ for the ground state ${^{1}}\Sigma^{+}$ for $HCO^{+}$. The constants are calculated based on experimentally measured Rydberg Series from the $3p\pi$ electronic state which converge to the rovibrational thresholds of the cation $(00^{0}0), (01^{1}0),(02^{0}0)$ and $(02^{2}0)$. Along with these thresholds, we use the experimentally measured $x_{23}$ anharmonic constant from Oka et al. and the theoretical $x_{12}$ anharmonic constant from Puzzarini et al. and Lee et al. To further characterize the bending coordinate anharmonicity of the potential energy surface of $HCO^{+}$, we assign Rydberg series obtained from the $3p \pi {^{2}}\Pi(030)\Sigma^{-} N^{\prime}=0$ and 2 converging to rovibrational thresholds $(03^{1}0)$ and $(03^{3}0)$ in the cation. From this extrapolation, we refine our anharmonic constants for the ground electronic state for $HCO^{-}$.
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Author Institution: Department of Chemistry, Purdue University