A quantum defect model for the s, p, d, and f Rydberg series of CaF
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JChemPhys_134_114313.pdf
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Author(s)
Kay, Jeffrey J.
Coy, Stephen L.
Wong, Bryan M.
Jungen, Christian
Field, Robert W.
Date Issued
March 2011
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Kay, Jeffrey J. et al. “A Quantum Defect Model for the S, P, D, and f Rydberg Series of CaF.” The Journal of Chemical Physics 134.11 (2011): 114313. © 2011 American Institute of Physics
Version
Final published version
Abstract
We present an improved quantum defect theory model for the “s,” “p,” “d,” and “f” Rydberg series of CaF. The model, which is the result of an exhaustive fit of high-resolution spectroscopic data, parameterizes the electronic structure of the ten (“s”Σ, “p”Σ, “p”Π, “d”Σ, “d”Π, “d”Δ, “f”Σ, “f”Π, “f”Δ, and “f”Φ) Rydberg series of CaF in terms of a set of twenty μ[subscript ℓℓ][superscript (Λ)] quantum defect matrix elements and their dependence on both internuclear separation and on the binding energy of the outer electron. Over 1000 rovibronic Rydberg levels belonging to 131 observed electronic states of CaF with n* ≥ 5 are included in the fit. The correctness and physical validity of the fit model are assured both by our intuition-guided combinatorial fit strategy and by comparison with R-matrix calculations based on a one-electron effective potential. The power of this quantum defect model lies in its ability to account for the rovibronic energy level structure and nearly all dynamical processes, including structure and dynamics outside of the range of the current observations. Its completeness places CaF at a level of spectroscopic characterization similar to NO and H[subscript 2].
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
http://dx.doi.org/10.1063/1.3565967
