## Files in this item

Files | Description | Format |
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application/vnd.openxmlformats-officedocument.presentationml.presentation 1179538.pptx (1MB) | Presentation | Microsoft PowerPoint 2007 |

application/pdf 3214.pdf (22kB) | Abstract |

## Description

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 |