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Published November 28, 2009 | Accepted Version + Supplemental Material
Journal Article Open

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

Abstract

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.

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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Accepted Version - nihms203896.pdf

Supplemental Material - b905554a.pdf

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August 19, 2023
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