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Influence of Hartree-Fock exchange on the calculated Mössbauer isomer shifts and quadrupole splittings in ferrocene derivatives using density functional theory

Nemykin, Victor N. and Hadt, Ryan G. (2006) Influence of Hartree-Fock exchange on the calculated Mössbauer isomer shifts and quadrupole splittings in ferrocene derivatives using density functional theory. Inorganic Chemistry, 45 (20). pp. 8297-8307. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180612-161524242

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Abstract

Influence of molecular geometry, type of exchange-correlation functional, and contraction scheme of basis set applied at the iron nuclei have been tested in the calculation of ^(57)Fe Mössbauer isomer shifts and quadrupole splittings for a wide range of ligand types, as well as oxidation and spin states, in inorganic and organometallic systems. It has been found that uncontraction of the s-part of Wachter's full-electron basis set at the iron nuclei does not appreciably improve the calculated isomer shifts. The observed correlations for all tested sets of geometries are close to each other and predominantly depend on the employed exchange-correlation functional with B3LYP functional being slightly better as compared to BPW91. Both hybrid (B3LYP) and pure (BPW91) exchange-correlation functionals are suitable for the calculation of isomer shifts in organometallic compounds. Surprisingly, it has been found that the hybrid B3LYP exchange-correlation functional completely fails in accurate prediction of quadrupole splittings in ferrocenes, while performance of the pure BPW91 functional for the same systems was excellent. This observation has been explained on the basis of relationship between the amount of Hartree-Fock exchange involved in the applied exchange-correlation functional and the calculated HOMO-LUMO energy gap in ferrocenes. On the basis of this explanation, use of only pure exchange-correlation functionals has been suggested for accurate prediction of Mössbauer spectra parameters in ferrocenes.


Item Type:Article
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https://doi.org/10.1021/ic061176qDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic061176qPublisherSupporting Information
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
Additional Information:© 2006 American Chemical Society. Received June 27, 2006. We thank Research Corporation (grant CC6766) and University of Minnesota (Grant-in-Aid to V.N.N.) for financial support and Minnesota Supercomputing Institute for the generous support of computer time. We also acknowledge Professor Eric Oldfield and Dr. Douglas Fox for the numerous discussions and interest.
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Funding AgencyGrant Number
Cottrell Scholar of Research CorporationCC6766
University of Minnesota DuluthUNSPECIFIED
Minnesota Supercomputing InstituteUNSPECIFIED
Issue or Number:20
Record Number:CaltechAUTHORS:20180612-161524242
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180612-161524242
Official Citation:Influence of Hartree−Fock Exchange on the Calculated Mössbauer Isomer Shifts and Quadrupole Splittings in Ferrocene Derivatives Using Density Functional Theory Victor N. Nemykin and Ryan G. Hadt Inorganic Chemistry 2006 45 (20), 8297-8307 DOI: 10.1021/ic061176q
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87043
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Jun 2018 14:43
Last Modified:03 Oct 2019 19:51

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