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

Jérôme Cuny; Kateryna Sykina; Bruno Fontaine; Laurent Le Pollès; Chris J. Pickard; Régis Gautier

doi:10.1039/C1CP22289A

⁹⁵Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters†

Jérôme Cuny,‡^a Kateryna Sykina,^a Bruno Fontaine,^a Laurent Le Pollès,^a Chris J. Pickard^b and Régis Gautier*^a

* Corresponding authors

^a 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
E-mail: rgautier@ensc-rennes.fr
Fax: +33 2 2323 8122
Tel: +33 2 2323 8122

^b Department of Physics & Astronomy, University College London, Gower Street, London WC1E 6BT, UK

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.

Supplementary files

Article information

DOI: https://doi.org/10.1039/C1CP22289A
Article type: Paper
Submitted: 13 Jul 2011
Accepted: 07 Sep 2011
First published: 29 Sep 2011

Download Citation

Phys. Chem. Chem. Phys., 2011,13, 19471-19479

Permissions

Request permissions

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

J. Cuny, K. Sykina, B. Fontaine, L. Le Pollès, C. J. Pickard and R. Gautier, Phys. Chem. Chem. Phys., 2011, 13, 19471 DOI: 10.1039/C1CP22289A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Physical Chemistry Chemical Physics

⁹⁵Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters†

Abstract

Supplementary files

Article information

Download Citation

Permissions

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

Social activity

Search articles by author

Spotlight

Advertisements

Physical Chemistry Chemical Physics