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

doi:10.1021/acs.jpca.6b07396

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

Chemistry

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

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 C_2v 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 language	English
Pages (from-to)	6963-6969
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	120
Issue number	35
DOIs	https://doi.org/10.1021/acs.jpca.6b07396
State	Published - Sep 8 2016

Bibliographical note

Funding Information:
This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant No. CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), and the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, through the Ames Laboratory Chemical Physics program (M.S.G. and M.W.S). The Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DE-AC02-07CH11358.

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1021/acs.jpca.6b07396

Cite this

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title = "Threshold Ionization and Spin-Orbit Coupling of Ceracyclopropene Formed by Ethylene Dehydrogenation",

abstract = "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.",

author = "Yuchen Zhang and Schmidt, {Michael W.} and Sudesh Kumari and Gordon, {Mark S.} and Yang, {Dong Sheng}",

note = "Funding Information: This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant No. CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), and the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, through the Ames Laboratory Chemical Physics program (M.S.G. and M.W.S). The Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DE-AC02-07CH11358. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Gordon, Mark S.

AU - Yang, Dong Sheng

N1 - Funding Information: This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant No. CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), and the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, through the Ames Laboratory Chemical Physics program (M.S.G. and M.W.S). The Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DE-AC02-07CH11358. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/9/8

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N2 - 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.

AB - 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.

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

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