Theoretical study on the photoelectron spectra of Ln(COT)2: Lanthanide dependence of the metal−ligand interaction

Erika Nakajo, Tomohide Masuda, Satoshi Yabushita

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Abstract

We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT)2 (Ln = La−Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e1g < e1u < e2g < e2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e2u symmetry. Because the magnitude of this 4f− ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

Original languageEnglish
Pages (from-to)9529-9544
Number of pages16
JournalJournal of Physical Chemistry A
Volume120
Issue number48
DOIs
Publication statusPublished - 2016 Jan 1

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Lanthanoid Series Elements
Photoelectrons
photoelectrons
orbitals
Ligands
Electron energy levels
Anions
Actinoid Series Elements
ligands
interactions
anions
Molecular orbitals
electron states
detachment
contraction
molecular orbitals
energy levels
analogs
energy
symmetry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical study on the photoelectron spectra of Ln(COT)2 : Lanthanide dependence of the metal−ligand interaction. / Nakajo, Erika; Masuda, Tomohide; Yabushita, Satoshi.

In: Journal of Physical Chemistry A, Vol. 120, No. 48, 01.01.2016, p. 9529-9544.

Research output: Contribution to journalArticle

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AB - We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT)2− (Ln = La−Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e1g < e1u < e2g < e2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e2u symmetry. Because the magnitude of this 4f− ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

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