Ground States, Excited States, and Metal-Ligand Bonding in Rare Earth Hexachloro Complexes: A DFT-Based Ligand Field Study

Atanasov, Mihail; Daul, Claude; Güdel, Hans U.; Wesolowski, Tomasz Adam; Zbiri, Mohamed

doi:10.1021/ic040105t

Scientific article

English

Ground States, Excited States, and Metal-Ligand Bonding in Rare Earth Hexachloro Complexes: A DFT-Based Ligand Field Study

Contributors

Atanasov, Mihail; Daul, Claude; Güdel, Hans U.; Wesolowski, Tomasz Adam; Zbiri, Mohamed

Published in

Inorganic chemistry, vol. 44, no. 8, p. 2954-2963

Publication date

2005

Abstract

Metal (4f)−ligand (Cl 3p) bonding in LnCl63- (Ln = Ce to Yb) complexes has been studied on the basis of 4f→4f and Cl,3p→4f charge-transfer spectra and on the analysis of these spectra within the valence bond configuration interaction model to show that mixing of Cl 3p into the Ln 4f ligand field orbitals does not exceed 1%. Contrary to this, Kohn−Sham formalism of density functional theory using currently available approximations to the exchange-correlation functional tends to strongly overestimate 4f−3p covalency, yielding, for YbCl63-, a much larger mixing of Cl 3p→4f charge transfer into the f13 ionic ground-state wave function. Thus, ligand field density functional theory, which was recently developed and applied with success to complexes of 3d metals in our group, yields anomalously large ligand field splittings for Ln, the discrepancy with experiment increasing from left to the right of the Ln 4f series. It is shown that eliminating artificial ligand-to-metal charge transfer in Kohn−Sham calculations by a procedure described in this work leads to energies of 4f−4f transitions in good agreement with experiment. We recall an earlier concept of Ballhausen and Dahl which describes ligand field in terms of a pseudopotential and give a thorough analysis of the contributions to the ligand field from electrostatics (crystal field) and exchange (Pauli) repulsion. The close relation of the present results with those obtained using the first-principles based and electron density dependent effective embedding potential is pointed out along with implications for applications to other systems.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Wesolowski

Citation (ISO format)

ATANASOV, Mihail et al. Ground States, Excited States, and Metal-Ligand Bonding in Rare Earth Hexachloro Complexes: A DFT-Based Ligand Field Study. In: Inorganic chemistry, 2005, vol. 44, n° 8, p. 2954–2963. doi: 10.1021/ic040105t

Article (Published version)

Identifiers

PID : unige:3623
DOI : 10.1021/ic040105t

Additional URL for this publication

http://pubs.acs.org/cgi-bin/article.cgi/inocaj/2005/44/i08/pdf/ic040105t.pdf

Journal ISSN

1939-5175

777views

1624downloads

Creation

02/10/2009 15:19:02

First validation

02/10/2009 15:19:02

Update

14/03/2023 15:15:42

Status update

14/03/2023 15:15:42

Last indexation

10/06/2025 21:31:04

Ground States, Excited States, and Metal-Ligand Bonding in Rare Earth Hexachloro Complexes: A DFT-Based Ligand Field Study

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

Main files (1)

Identifiers

Additional URL for this publication

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation