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Issue 30, 2009
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A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

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Abstract

The electronic states of CeCp3+ have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous conclusion that bands A and D in the valence photoelectron spectrum, despite their 3.2 eV separation, are produced by ionization of the single 4f electron of CeCp3 [M. Coreno, M. de Simone, J. C. Green, N. Kaltsoyannis, N. Narband and A. Sella, Chem. Phys. Lett., 432, 2006, 17]. The origin of this effect is probed using the CASSCF/CASPT2 approach. While configurations based on the canonical CASSCF orbitals are found to be an unreliable description of the ground and excited states of CeCp3+, the state-specific natural orbitals and their occupations yield greater insight, allowing us to characterize ion states in terms of the presence or otherwise of a Ce 4f-localised electron. Neither the CeCp3+ ground state (assigned to band A), and two excited states (Image ID:b902263e-t1.gif1A′ and 1A″, associated with band D), possess such a metal-based electron, as expected of f ionization. The Image ID:b902263e-t2.gif1A′ and 1A′′ states differ from the ground state in having a significant Ce 5d population, arising from Cp → Ce charge transfer, which accompanies f ionization, and which is responsible for the energetic separation of bands A and D in the valence photoelectron spectrum.

Graphical abstract: A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

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Publication details

The article was received on 03 Feb 2009, accepted on 03 Jun 2009 and first published on 23 Jun 2009


Article type: Paper
DOI: 10.1039/B902263E
Citation: Dalton Trans., 2009, 5943-5953
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    A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

    R. Coates, M. Coreno, M. DeSimone, J. C. Green, N. Kaltsoyannis, A. Kerridge, N. Narband and A. Sella, Dalton Trans., 2009, 5943
    DOI: 10.1039/B902263E

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