Multi-channel quantum defect theory calculation of vibrational autoionization resonance width of v=1, n* ≈ 14 CaF rydberg state

Field, Robert W.

Permalink

https://hdl.handle.net/2142/100621 Copy

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

Issue Date

2018-06-18

Keyword(s)

Mini-symposium: New Ways of Understanding Molecular Spectra

Abstract

Vibrational auto-ionization resonance widths (γ) of v = 1, n ∗ ≈ 14 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 pΠ eigen-channel has the shortest vibrational auto-ionization lifetime, ∼10 ps, which is at least 4× 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 γ of the 14.36 pΠ− rotational sequence (where the superscript ‘-’ indicates negative Kronig symmetry) are nearly N-independent, while those of the 14.36 pΠ+ rotational sequence (where the superscript ‘+’ indicates positive Kronig symmetry) decrease quickly as a function of N, i.e. γ(N = 10) ≈ 1 2 γ(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 γ for the 14.36 pΠ+ 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.36pΠ eigen-channel is explained based on the electronic properties of its valance-precursor state, the C 2Π state, for which the electron density is polarized toward the fluorine atom.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/100621

DOI

10.15278/isms.2018.MH06

Copyright and License Information

Copyright 2018 Robert W. Field

Owning Collections