Threshold Ionization and Spin-Orbit Coupling of Ceracyclopropene Formed by Ethylene Dehydrogenation

Yuchen Zhang, Michael W. Schmidt, Sudesh Kumari, Mark S. Gordon, Dong Sheng Yang

Research output: Contribution to journalArticlepeer-review

15 Scopus citations


A Ce atom reaction with ethylene was carried out in a laser-vaporization metal cluster beam source. Ce(C2H2) formed by hydrogen elimination from ethylene was investigated by mass-analyzed threshold ionization (MATI) spectroscopy, isotopic substitutions, and relativistic quantum chemical computations. The theoretical calculations include a scalar relativistic correction, dynamic electron correlation, and spin-orbit coupling. The MATI spectrum exhibits two nearly identical band systems separated by 128 cm-1. The separation is not affected by deuteration. The two-band systems are attributed to spin-orbit splitting and the vibrational bands to the symmetric metal-ligand stretching and in-plane carbon-hydrogen bending excitations. The spin-orbit splitting arises from interactions of a pair of nearly degenerate triplets and a pair of nearly degenerate singlets. The organolanthanide complex is a metallacyclopropene in C2v symmetry. The low-energy valence electron configurations of the neutral and ion species are Ce 4f16s1 and Ce 4f1, 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 5d Ce orbital and a π∗ antibonding orbital of acetylene.

Original languageEnglish
Pages (from-to)6963-6969
Number of pages7
JournalJournal of Physical Chemistry A
Issue number35
StatePublished - Sep 8 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


Dive into the research topics of 'Threshold Ionization and Spin-Orbit Coupling of Ceracyclopropene Formed by Ethylene Dehydrogenation'. Together they form a unique fingerprint.

Cite this