Ligand-field theory applied to diatomic transition metals. Results for the d?Ad?B?? states of Ni?, the d?Nid??cu?? states of NiCu, and the d?Ni(?F)d??cu???*? excited states of NiCu

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Publication Type Journal Article
School or College College of Science
Department Chemistry
Creator Morse, Michael David
Other Author Spain, Eileen M.
Title Ligand-field theory applied to diatomic transition metals. Results for the d?Ad?B?? states of Ni?, the d?Nid??cu?? states of NiCu, and the d?Ni(?F)d??cu???*? excited states of NiCu
Date 1992
Description A ligand-field theory has been developed for transition-metal diatomics having electronic configurations of d?Ad??B??, d?Ad?B?? and d?A(?F)d??B???*?. The theory treats each atom as a point charge and includes spin-orbit interactions. No contributions due to d-orbital chemical bonding are included. Since the d orbitals are quite small compared to the bond lengths in these molecules, the only inputs to the theory are the ligand charges (ZA and ZB), the radial expectation values {r?A} nd, {r?B}nd, {r?A} nd, and {r?B} nd, the atomic spin-orbit parameters A and B, and the bond length, R. Calculations employing no adjustable parameters (setting ZA,B = + 1.0, and using radial expectation values and spin-orbit parameters from atomic tables) provide essentially quantitative agreement with ab initio results on the d?Nid??Cu?? manifold of states in NiCu, and on the d?Ad?B?? manifold of states in Ni2. This demonstrates that the ligand-field model has some validity for metal molecules containing nickel, primarily because of the compact nature of the 3d orbitals in this element. Similar calculations of the d?Ad?B?? manifold of states in Pt?, and the d?Ni?Pt?? manifold of states in NiPt are presented for comparison to future ab initio or experimental measurements, although the possibility of d-orbital contributions to the bonding in these species makes the ligand-field model less favorable in these examples. The d?Ni(?F)d??Cu???*? excited electronic states of NiCu, which are well known from resonant two-photon ionization spectroscopy, are also investigated in the ligandfield model. As a final example, the d?Ni(?F)d??Cu???*?? excited electronic states of NiH are also examined using the same treatment as that employed for the d?Ni(?F)d??Cu???*? excited manifold of NiCu.
Type Text
Publisher American Institute of Physics (AIP)
Volume 97
Issue 7
First Page 4641
Last Page 4660
DOI 10.1063/1.463867
Language eng
Bibliographic Citation Spain, E. M., & Morse, M. D. (1992). Ligand-field theory applied to diatomic transition metals. Results for the d?Ad?B?? states of Ni?, the d?Nid??cu?? states of NiCu, and the d?Ni(?F)d??cu???*? excited states of NiCu. Journal of Chemical Physics, 97(7), 4641-60.
Rights Management ©American Institute of Physics. The following article appeared in Spain, E. M., & Morse, M. D. (1992). Ligand-field theory applied to diatomic transition metals. Results for the d?Ad?B?? states of Ni?, the d?Nid??cu?? states of NiCu, and the d?Ni(?F)d??cu???*? excited states of NiCu. Journal of Chemical Physics, 97(7), 4641-60. and may be found at http://dx.doi.org/10.1063/1.463867.
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Identifier ir-main,16998
ARK ark:/87278/s6nk3z57
Setname ir_uspace
Date Created 2012-06-13
Date Modified 2012-06-13
ID 702836
Reference URL https://collections.lib.utah.edu/ark:/87278/s6nk3z57
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