A Caltech Library Service

Ligand-Field Excited States of Metal Hexacarbonyls

Hummel, Patrick and Oxgaard, Jonas and Goddard, William A., III and Gray, Harry B. (2005) Ligand-Field Excited States of Metal Hexacarbonyls. Inorganic Chemistry, 44 (7). pp. 2454-2458. ISSN 0020-1669. doi:10.1021/ic048215n.

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item:


Over 35 years ago, the low-lying bands in the absorption spectra of metal hexacarbonyls were assigned to ligand-field (LF) excitations. Recent time-dependent density functional theory (TDDFT) calculations on M(CO)_6 (M = Cr, Mo, W) are not in accord with this interpretation. Here we extend TDDFT calculations to the isoelectronic series V(CO)_6^-, Cr(CO)_6, and Mn(CO)_6^+. By analyzing the trends in the energies of the various electronic excitations, we are able to fully assign the spectra of the complexes. In particular, we demonstrate that the LF excitation ^1A_(1g) → ^1T_(1g) is observed at 4.12 eV in the Mn(CO)_6^+ spectrum, but all LF features in the spectra of V(CO)_6^- and Cr(CO)_6 are obscured by intense metal-to-ligand charge-transfer absorptions. Our results suggest that use of B3LYP as the exchange-correlation functional and inclusion of solvation effects through a continuum solvation model lead to the most accurate calculated transition energies.

Item Type:Article
Related URLs:
URLURL TypeDescription
Goddard, William A., III0000-0003-0097-5716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2005 American Chemical Society. Received December 17, 2004. Publication Date (Web): March 3, 2005. We thank the Caltech Summer Undergraduate Research Fellowship program as well as DARPA-PROM, ONR-DURIP, ARO-DURIP, Beckman Institute, and NSF-MRI for support.
Funding AgencyGrant Number
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20170315-102857802
Persistent URL:
Official Citation:Ligand-Field Excited States of Metal Hexacarbonyls Patrick Hummel, Jonas Oxgaard, William A. Goddard III, and Harry B. Gray Inorganic Chemistry 2005 44 (7), 2454-2458 DOI: 10.1021/ic048215n
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75142
Deposited By: Tony Diaz
Deposited On:15 Mar 2017 18:09
Last Modified:15 Nov 2021 16:31

Repository Staff Only: item control page