TY - JOUR
T1 - Threshold Ionization and Spin-Orbit Coupling of Ceracyclopropene Formed by Ethylene Dehydrogenation
AU - Zhang, Yuchen
AU - Schmidt, Michael W.
AU - Kumari, Sudesh
AU - Gordon, Mark S.
AU - Yang, Dong Sheng
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/8
Y1 - 2016/9/8
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.
UR - http://www.scopus.com/inward/record.url?scp=84986272563&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84986272563&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.6b07396
DO - 10.1021/acs.jpca.6b07396
M3 - Article
AN - SCOPUS:84986272563
SN - 1089-5639
VL - 120
SP - 6963
EP - 6969
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 35
ER -