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A quantum defect model for the *s*, *p*, *d*, and *f* Rydberg series of CaF

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10.1063/1.3565967

### 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 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 H2.

© 2011 American Institute of Physics

Received 20 September 2010
Accepted 18 February 2011
Published online 18 March 2011
Corrected 30 January 2012

Acknowledgments: We gratefully acknowledge financial support for this work from the United States National Science Foundation (NSF) under Grant Nos. CHE-0749821 and CHE-1058709.1.

Article outline:

I. INTRODUCTION

II. EXPERIMENT

III. THEORY

IV. RESULTS AND DISCUSSION

A. Application to CaF

B. Fit procedure

1. Initialization and convergence using *and*

2. Generation of estimates of

3. Convergence using *,* , and

4. Refinement by addition of second derivatives: *,* , and

C. Quantum defect matrices and quality of fit

D. **R**-matrix estimates of quantum defect matrix elements

V. CONCLUSIONS

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2011-03-18

2014-04-17

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