TITLE

A multichannel quantum defect fit to the n*=6–8 core-penetrating s∼p∼d supercomplexes of CaF

AUTHOR(S)
Murphy, James E.; Friedman-Hill, Ernest; Field, Robert W.
PUB. DATE
October 1995
SOURCE
Journal of Chemical Physics;10/15/1995, Vol. 103 Issue 15, p6459
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The spectrum of the core-penetrating s, p, and d Rydberg series of calcium monofluoride between n*=6 and 8 have been analyzed using multichannel quantum defect theory (MQDT). From least-squares fits of the n*=6, 7, and 8 (-) Kronig symmetry p∼d supercomplexes we have determined B+ (the rotational constant of CaF+) to be 0.3729 cm-1, the mixing coefficients between the pπ and dπ series (the 0.98 Π series is 41% p and 59% d while the 0.35 Π series is 41% d and 59% p), and the eigenchannel (rotationless) quantum defects of the 0.98 Π, 0.35 Π, and 0.14 Δ series. A similar MQDT fit was attempted for the (+) Kronig symmetry s∼p∼d supercomplexes, but the mixing coefficients for the σ series could not be determined even though the mixing coefficients for the π series were as well determined as in the fit to the (-) symmetry series. The failure of the s∼p∼d model to fit the (+) symmetry series, particularly the σ series, is an indication that, for the (+) symmetry series, mixing of the sσ, pσ, and dσ series with the fσ series must be considered. Experiments are currently under way to observe and characterize the f σ, π, δ, γ series so that an s∼p∼d∼f supercomplex model can be developed for the (+) symmetry series. © 1995 American Institute of Physics.
ACCESSION #
7649467

 

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