95Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters.Report as inadecuate




95Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters. - Download this document for free, or read online. Document in PDF available to download.

* Corresponding author 1 ISCR - Institut des Sciences Chimiques de Rennes 2 Department of Physics and Astronomy London

Abstract : Solid-state 95Mo nuclear magnetic resonance NMR properties of molybdenum hexacarbonyl have been computed using density functional theory DFT based methods. Both quadrupolar coupling and chemical shift parameters were evaluated and compared with parameters of high precision determined using single-crystal 95Mo NMR experiments. Within a molecular approach, the effects of major computational parameters, i.e. basis set, exchange-correlation functional, treatment of relativity, have been evaluated. Except for the isotropic parameter of both chemical shift and chemical shielding, computed NMR parameters are more sensitive to geometrical variations than computational details. Relativistic effects do not play a crucial part in the calculations of such parameters for the 4d transition metal, in particular isotropic chemical shift. Periodic DFT calculations were tackled to measure the influence of neighbouring molecules on the crystal structure. These effects have to be taken into account to compute accurate solid-state 95Mo NMR parameters even for such an inorganic molecular compound.





Author: Jérôme Cuny - Kateryna Sykina - Bruno Fontaine - Laurent Le Pollès - Chris J. Pickard - Régis Gautier -

Source: https://hal.archives-ouvertes.fr/



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