title: 95Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters.
abstract: Solid-state (95)Mo 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 (95)Mo 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 (95)Mo NMR parameters even for such an inorganic molecular compound.
authors.affiliation: Sciences Chimiques de Rennes, UMR 6226, CNRS - Ecole Nationale Supérieure de Chimie de Rennes, Avenue du Général Leclerc, CS 50837, 35708 Rennes cedex 7, France.
authors.forename: Jérôme
authors.initials: J
authors.lastname: Cuny
authors.forename: Kateryna
authors.initials: K
authors.lastname: Sykina
authors.forename: Bruno
authors.initials: B
authors.lastname: Fontaine
authors.forename: Laurent
authors.initials: L
authors.lastname: Le Pollès
authors.forename: Chris J
authors.initials: CJ
authors.lastname: Pickard
authors.forename: Régis
authors.initials: R
authors.lastname: Gautier