THE RYDBERG STATES OF NO.
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Date
1965
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Ohio State University
Abstract
The interpretation of the lowest Rydberg states of NO given recently by Huber and $Miescher^{1}$ has been fully confirmed by the identification in the absorption spectrum, of several higher members of the proposed Rydberg $series.^{2}$ The exceedingly complex spectrum can now be interpreted, owing to the work of Miescher and his $collaborators,^{3}$ in terms of a relatively simple electronic energy level diagram. The pattern of Rydberg states resembles strongly that of an atom with closed-shell core. The molecular states corresponding to atomic p- and d- states split into components with different $\lambda$, but in NO the sign of this splitting is opposite to the one expected and found in Rydberg states of $H_{2}^{+}, H_{2}, He_{2}, N_{2}$, and CO. The pattern observed in NO has been reproduced rather well in the recent theoretical calculation by LeFebvre-Brion and $Moser^{4}$ who have taken into account the configuration interaction between the unoccupied (Rydberg-) orbitals though they have not included the interaction with excited valence-shell configurations. The relative absorption intensities of the Rydberg bands and the interactions with non-Rydberg states are well explained by the assignment of approximate $g-$ and $u-$ symmetries to the states of the nearly symmetric NO molecule. The $p-$ type Rydberg states of configurations $np\sigma_{u}$ and $np\pi_{u}$ appear with much greater absorption intensities than those resembling atomic $s-$ and $d-$ states and they interact strongly with the non-Rydberg states $^{2}H_{u}$ and with the repulsive state $(\sigma_{u} 2p) ^{2}\Sigma_{u}^{+}$. These and other observations confirm that it is meaningful to describe the lowest Rydberg states of NO with quantum numbers 3s, 3p, 3d of an atom with a closed $n=2$ -shell core such as Boron or Sodium.
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This work was supported by NASA Grant NsG-414.
Author Institution: Department of Astrophysical Sciences, Princeton University
Author Institution: Department of Astrophysical Sciences, Princeton University