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

Nyambo, Silver

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

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

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

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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