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Paper
Phys. Chem. Chem. Phys., 2009, 11, 10377 - 10384, DOI: 10.1039/b905554a
Comparative calculation of EPR spectral parameters in [MoVOX4]-, [MoVOX5]2-, and [MoVOX4(H2O)]- complexes
Ryan G. Hadt, Victor N. Nemykin, Joseph G. Olsen and Partha Basu
The EPR spectral parameters, i.e.g-tensors and molybdenum hyperfine couplings, for several d1 systems of the general formula [MoVEX4]n-, [MoVOX5]2-, and [MoVOX4(H2O)]- (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 EMo–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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