MASS-ANALYZED THRESHOLD IONIZATION SPECTROSCOPY AND SPIN-ORBIT COUPLING OF CERIUM-HYDROCARBON COMPLEXES

Zhang, Yuchen

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https://hdl.handle.net/2142/96808 Copy

Description

Title

MASS-ANALYZED THRESHOLD IONIZATION SPECTROSCOPY AND SPIN-ORBIT COUPLING OF CERIUM-HYDROCARBON COMPLEXES

Author(s)

Zhang, Yuchen

Contributor(s)

• Yang, Dong-Sheng
• Gordon, Mark S
• Schmidt, Michael W
• Kumari, Sudesh

Issue Date

6/23/2017

Keyword(s)

Ions

Abstract

Ce(C$_{2}$H$_{2}$) and Ce(C$_{4}$H$_{6}$) are produced by the Ce-mediated ethylene activation and investigated by mass-analyzed threshold ionization (MATI) spectroscopy, isotopic substitutions, and relativistic quantum chemical computations. The MATI spectrum of Ce(C$_{2}$H$_{2}$) exhibits two nearly identical band systems separated by 128 wn, and that of Ce(C$_{4}$H$_{6}$) shows three similar band systems separated by 55 and 105 wn. These separations are not affected by deuteration. The observed band systems for the two Ce-hydrocarbon species are attributed to the spin-orbit splitting arising from interactions of triplet and singlet states. Ce(C$_{2}$H$_{2}$) is a metallacyclopropene in C$_{2v}$ symmetry, and Ce(C$_{4}$H$_{6}$) is a metallacyclopentene in C$_{s}$ symmetry. The low-energy valence electron configurations of the neutral and ionic states of each species are Ce 4f$^{1}$6s$^{1}$ and Ce 4f$^{1}$, respectively. The remaining two electrons that are associated with the isolated Ce atom or ion are spin paired in a molecular orbital that is a bonding combination between a Ce 5d orbital and a hydrocarbon $pi$* antibonding orbital.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/96808

DOI

10.15278/isms.2017.FE03

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