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Title:MULTI-CHANNEL QUANTUM DEFECT THEORY CALCULATION OF VIBRATIONAL AUTOIONIZATION RESONANCE WIDTH OF v=1, n* ≈ 14 CaF RYDBERG STATE
Author(s):Field, Robert W.
Contributor(s):Barnum, Timothy J.; Jiang, Jun
Subject(s):Mini-symposium: New Ways of Understanding Molecular Spectra
Abstract:Vibrational auto-ionization resonance widths ($\gamma$) of $v=1$, $n^*\approx14$ Rydberg states of CaF are calculated in this work, based on results of a global multi-channel quantum defect fit. The calculation indicates that the $n$.36 $p\Pi$ eigen-channel has the shortest vibrational auto-ionization lifetime, $\sim$10 $p$s, which is at least $4\times$ shorter than the lifetime of all other CaF eigen-channels, in agreement with experimental observations. In addition, the calculation successfully reproduces the experimental observations that $\gamma$ of the 14.36 $p\Pi^-$ rotational sequence (where the superscript `-' indicates negative Kronig symmetry) are nearly $N$-independent, while those of the 14.36 $p\Pi^+$ rotational sequence (where the superscript `+' indicates positive Kronig symmetry) decrease quickly as a function of $N$, i.e. $\gamma (N=10) \approx \frac{1}{2} \gamma (N=1)$. By examining the eigen-channel composition of the two rotational sequences of state of opposite Kronig symmetry, we are able to show that the significantly faster decrease of $\gamma$ for the 14.36 $p\Pi^+$ rotational sequence is caused by the stronger $l$-uncoupling interaction in the positive Kronig symmetry manifold. Based on a valence-precursor model (first suggested by Mulliken), the significantly faster vibrational auto-ionization rate of the $n.36 p\Pi$ eigen-channel is explained based on the electronic properties of its valance-precursor state, the $C^2\Pi$ state, for which the electron density is polarized toward the fluorine atom.
Issue Date:06/18/18
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/100621
DOI:10.15278/isms.2018.MH06
Other Identifier(s):MH06
Date Available in IDEALS:2018-08-17
2018-12-12


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