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Comparative calculation of EPR spectral parameters in [Mo^VOX_4]^-, [Mo^VOX_5]^(2-), and [Mo^VOX_4(H_2O)]^- complexes

Hadt, Ryan G. and Nemykin, Victor N. and Olsen, Joseph G. and Basu, Partha (2009) Comparative calculation of EPR spectral parameters in [Mo^VOX_4]^-, [Mo^VOX_5]^(2-), and [Mo^VOX_4(H_2O)]^- complexes. Physical Chemistry Chemical Physics, 11 (44). pp. 10377-10384. ISSN 1463-9076. PMCID PMC2879133. doi:10.1039/b905554a.

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The EPR spectral parameters, i.e. g-tensors and molybdenum hyperfine couplings, for several d^1 systems of the general formula [Mo^VEX_4]^(n-), [Mo^VOX_5]^(2-), and [Mo^VOX_4(H_2O)]^- (E = O, N; X = F, Cl, Br; n = 1 or 2) were calculated using Density Functional Theory. The influence of basis sets, their contraction scheme, the type of exchange-correlation functional, the amount of Hartree-Fock exchange, molecular geometry, and relativistic effects on the calculated EPR spectra parameters have been discussed. The g-tensors and molybdenum hyperfine coupling parameters were calculated using a relativistic Hamiltonian coupled with several LDA, GGA, and 'hybrid' exchange-correlation functionals and uncontracted full-electron DGauss DZVP basis sets. The calculated EPR parameters are found to be sensitive to the Mo=E distance and E=Mo-Cl angle, and thus the choice of starting molecular geometry should be considered as an important factor in predicting the g-tensors and hyperfine coupling constants in oxo-molybdenum compounds. In the present case, the GGA exchange-correlation functionals provide a better agreement between the theory and the experiment.

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Hadt, Ryan G.0000-0001-6026-1358
Alternate Title:Comparative calculation of EPR spectral parameters in [MoVOX4]−, [MoVOX5]2−, and [MoVOX4(H2O)]− complexes
Additional Information:© the Owner Societies 2009. Received 19th March 2009, Accepted 11th September 2009. First published on 30th September 2009. We thank the National Science Foundation (Grant CHE-0809203) as well as the National Institute of Health (GM 650155 to PB) for financial support and the Minnesota Supercomputing Institute for the generous support of computer time, as well as Undergraduate Research opportunity grants to RH and JO.
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University of Minnesota DuluthUNSPECIFIED
Issue or Number:44
PubMed Central ID:PMC2879133
Record Number:CaltechAUTHORS:20180612-140553392
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87018
Deposited By: George Porter
Deposited On:12 Jun 2018 21:19
Last Modified:15 Nov 2021 20:44

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