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Density‐Functional Calculation of the 183 W and 17 O NMR Chemical Shifts for Large Polyoxotungstates
Author(s) -
Gracia Jose,
Poblet Josep M.,
Autschbach Jochen,
Kazansky Leonid P.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500832
Subject(s) - chemistry , chemical shift , paramagnetism , crystallography , density functional theory , tungsten , diamagnetism , atomic orbital , computational chemistry , physics , condensed matter physics , organic chemistry , quantum mechanics , magnetic field , electron
A phosphane sulfate relativistic DFT method (ZORA)has been used to calculate the 183 W and 17 O NMR chemicalshifts for large polyoxotungstates, including W 6 O 19 2– ,CH 3 OTiW 5 O 18 3– , W 5 O 18 W II NO 3– , W 10 O 32 4– , α‐δ‐γ‐XW 12 O 40 n – , β‐PW 9 O 28 Br 6 3– , P 2 W 18 O 62 6– , PW 2 O 14 3– , and W 7 O 24 6– , based on their optimized molecular structures. Despite sizeable deviations between the calculated and experimental values, the calculations correctly reproduce the trends in the change of the chemical shift for both nuclei. As expected, the diamagnetic term is almost constant throughout the whole series. The change in the chemical shifts is shown to be determined by the paramagnetic term, which depends on the electronic structure of the whole anion under study and, in particular, on the local geometry around a given tungsten atom. On the other hand, there is no correlation between the chemical shift and HOMO–LUMO gap, showing that deeper occupied levels and several unoccupied orbitals play an important role in the paramagnetic term. However, analysis of the components of the paramagnetic shielding has shown that the most significant transitions determining the change of both 183 W and 17 O NMR chemical shifts for anions consisting of tungsten and oxygen atoms are the occupied–occupied and not the occupied–virtual ones.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)