Abstract
We have investigated the computation of 17O NMR chemical shifts of a wide range of polyoxometalates using density functional theory. The effects of basis sets and exchange-correlation functionals are explored, and whereas pure DFT functionals generally predict the chemical shifts of terminal oxygen sites quite well, hybrid functionals are required for the prediction of accurate chemical shifts in conjunction with linear regression. By using PBE0/def2-tzvp//PBE0/cc-pvtz(H-Ar), lanl2dz(K-) we have computed the chemical shifts of 37 polyoxometalates, corresponding to 209 17O NMR signals. We also show that at this level of theory the protonation-induced pH dependence of the chemical shift of the triprotic hexaniobate Lindqvist anion, [HxNb6O19](8-x), can be reproduced, which suggests that hypotheses regarding loci of protonation can be confidently tested.
| Original language | English |
|---|---|
| Pages (from-to) | 8235-8241 |
| Number of pages | 7 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 18 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 21 Mar 2016 |
Cite this
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Predicting 17O NMR chemical shifts of polyoxometalates using density functional theory. / Sharma, Rupali; Zhang, Jie; Ohlin, C André.
In: Physical Chemistry Chemical Physics, Vol. 18, No. 11, 21.03.2016, p. 8235-8241.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Predicting 17O NMR chemical shifts of polyoxometalates using density functional theory
AU - Sharma, Rupali
AU - Zhang, Jie
AU - Ohlin, C André
PY - 2016/3/21
Y1 - 2016/3/21
N2 - We have investigated the computation of 17O NMR chemical shifts of a wide range of polyoxometalates using density functional theory. The effects of basis sets and exchange-correlation functionals are explored, and whereas pure DFT functionals generally predict the chemical shifts of terminal oxygen sites quite well, hybrid functionals are required for the prediction of accurate chemical shifts in conjunction with linear regression. By using PBE0/def2-tzvp//PBE0/cc-pvtz(H-Ar), lanl2dz(K-) we have computed the chemical shifts of 37 polyoxometalates, corresponding to 209 17O NMR signals. We also show that at this level of theory the protonation-induced pH dependence of the chemical shift of the triprotic hexaniobate Lindqvist anion, [HxNb6O19](8-x), can be reproduced, which suggests that hypotheses regarding loci of protonation can be confidently tested.
AB - We have investigated the computation of 17O NMR chemical shifts of a wide range of polyoxometalates using density functional theory. The effects of basis sets and exchange-correlation functionals are explored, and whereas pure DFT functionals generally predict the chemical shifts of terminal oxygen sites quite well, hybrid functionals are required for the prediction of accurate chemical shifts in conjunction with linear regression. By using PBE0/def2-tzvp//PBE0/cc-pvtz(H-Ar), lanl2dz(K-) we have computed the chemical shifts of 37 polyoxometalates, corresponding to 209 17O NMR signals. We also show that at this level of theory the protonation-induced pH dependence of the chemical shift of the triprotic hexaniobate Lindqvist anion, [HxNb6O19](8-x), can be reproduced, which suggests that hypotheses regarding loci of protonation can be confidently tested.
UR - http://www.scopus.com/inward/record.url?scp=84960473425&partnerID=8YFLogxK
UR - http://pubs.rsc.org.ezproxy.lib.monash.edu.au/en/content/articlepdf/2016/cp/c5cp07766d?page=search
U2 - 10.1039/c5cp07766d
DO - 10.1039/c5cp07766d
M3 - Article
AN - SCOPUS:84960473425
VL - 18
SP - 8235
EP - 8241
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 11
ER -