University of Illinois Urbana-Champaign

MATI spectroscopy of Ln(OH)2 (Ln = La AND Ce) formed by O-H bond activation of water

Nyambo, Silver

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1380654.pptx
3762.pdf

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https://hdl.handle.net/2142/104234

Description

Title
MATI spectroscopy of Ln(OH)2 (Ln = La AND Ce) formed by O-H bond activation of water
Author(s)
Nyambo, Silver
Contributor(s)
  • Yang, Dong-Sheng
  • Zhang, Yuchen
  • Karna, Priya
  • Kim, Jong Hyun
Issue Date
2019-06-19
Keyword(s)
Metal containing
Date of Ingest
  • 2019-07-15T22:16:26Z
  • 2020-01-25T19:29:18Z
Abstract
Lanthanide (Ln = La and Ce) atom reactions with water are carried out in a pulsed-laser ablation molecular beam source and characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. Both reactions yield Ln(OH)$_{2}$ as the main product through a hydrogen atom elimination of each water molecule. The MATI spectra of Ln(OH)$_{2}$ are dominated by the origin band and metal-ligand symmetric stretching and bending vibronic progressions. Adiabatic ionization energies measured from the spectra are 40135 (5) \wn for La(OH)$_{2}$ and 40756 (5) \wn for the Ce(OH)$_{2}$. The molecular symmetry of Ln(OH)$_{2}$ is C$_{2}$$_{v}$, and the observed transitions are $^{1}$A$_{1}$ - $^{2}$A$_{1}$ for La(OH)$_{2}$ and $^{2}$B$_{1}$ - $^{3}$B$_{1}$ for Ce(OH)$_{2}$. The ground valence electron configurations of La(OH)$_{2}$ and Ce(OH)$_{2}$ are La 6s$^{1}$ and Ce 4f$^{1}$6s$^{1}$, respectively. Ionization of each species removes a Ln 6s-based electron, and the resultant ion also has C$_{2}$$_{v}$ symmetry. The spectrum of Ce(OH)$_{2}$ has a broader linewidth than that of La(OH)$_{2}$, which is attributed to the unresolved spin-orbit levels by comparing with relativistic quantum calculations at the level of spin-orbit multi-reference quasi-degenerated perturbation theory. The metal-mediated hydrogen elimination of water is predicted to be thermodynamically and kinetically favorable by the density functional theory calculations.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Permalink
http://hdl.handle.net/2142/104234
DOI
https://doi.org/10.15278/isms.2019.WJ10
Copyright and License Information
Copyright 2019 Silver Nyambo

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Abstracts & Presentations - 2019 International Symposium on Molecular Spectroscopy PRIMARY