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Computational Modeling of Polyoxotungstates by Relativistic DFT Calculations of ^183^W NMR Chemical Shifts by Alessandro Bagno; Marcella Bonchio; Jochen Autschbach is a Chemistry article available to read on EtoBox.

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## Abstract The ^183^W nuclear shielding in a variety of tungsten polyoxometalates (POM) (Lindqvist, Anderson, decatungstates, Keggin) of different shapes and charges has been modeled by DFT calculations that take into account relativistic effects, by means of the zero‐order regular approximation (ZORA), and solvent effects, by the conductor‐like screening model (COSMO) continuum method. The charge/surface area ratio (__q__/__A__) is proposed as an indicator of the charge density to which the solvation energies of all POMs are correlated in a satisfactory way. Among the various theoretical levels tested (ZORA scalar or spin‐orbit, frozen‐core or all‐electron basis set, geometry optimization in the gas phase or in the continuum solvent, etc.), the best results are obtained when both geometry optimization in solvent and spin‐orbit shielding are included (mean absolute error of __δ__=35 ppm). The quality of the computed chemical shifts depends systematically on the charge density as expressed by __q__/__A__; thus, POMs with low __q__/__A__ ratios display the best agreement with experimental data. The performance of the method is such that computed values can aid the assignment of the

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Author

Alessandro Bagno; Marcella Bonchio; Jochen Autschbach

Publisher

Wiley

Published

2006

Field

Chemistry (Physical Sciences)