Rydberg states with a 2Π core: The b3Πi and C1Π states of DCl

  1. Get@NRC: Rydberg states with a 2Π core: The b3Πi and C1Π states of DCl (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1016/0022-2852(83)90276-X
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Journal titleJournal of Molecular Spectroscopy
Pages387404; # of pages: 18
AbstractThe rotational structure in the lowest Rydberg complex of hydrogen chloride, [X2Π]4sσ, was reinvestigated. The study is limited to the spectrum of D35Cl, the HCl bands being too diffuse for a detailed analysis of second-order effects. The Λ-type doubling in both component states, b3Πi and C1Π, is small since it arises from the uncoupling of the core rather than Rydberg orbital angular momentum. It can be interpreted in terms of pure precession relations that are known to exist between the ground and first excited states of DCl+. By contrast, the spin-orbit interactions, also originating in the core, are strong. In addition to distorting the triplet splitting in b3Π, they lead to an avoided crossing between the nearly coinciding levels b3Π0 (v = 1) and C1Π1 (v = 0). They are also responsible for anomalies in the b3Π0 ← X1Σ+R-branch intensities of DCl as well as of HBr, DBr, and HI. From the J values at the observed R-branch minima we have estimated the ratio of the transition moments associated with the excitation of a 3pσ or 3pπ core electron to the 4sσ Rydberg orbital of DCl and, correspondingly, of the other hydrogen halides.
Publication date
AffiliationNRC Herzberg Institute of Astrophysics; National Research Council Canada
Peer reviewedYes
NRC number20909
NPARC number21275094
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Record identifier8ce4c458-c0a0-42a2-979c-64be536200b6
Record created2015-05-07
Record modified2016-05-09
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