Research output: Contribution to Journal/Magazine › Journal article › peer-review
A first-principles computational O-17 NMR investigation of metal ion-oxygen interactions in carboxylate oxygens of alkali oxalates. / Wong, Alan; Thurgood, Gary; Dupree, Ray et al.
In: Chemical Physics Letters, Vol. 337, No. 1-3, 01.08.2007, p. 144-150.Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - A first-principles computational O-17 NMR investigation of metal ion-oxygen interactions in carboxylate oxygens of alkali oxalates
AU - Wong, Alan
AU - Thurgood, Gary
AU - Dupree, Ray
AU - Smith, Mark E.
PY - 2007/8/1
Y1 - 2007/8/1
N2 - O-17 NMR parameters, including chemical shift (CS) and electrical-field gradient (EFG) tensors, are calculated for oxalate compounds containing various different alkali ions using a DFT infinite periodic solid approach. This DFT study allows correlations to be found between the metal ion and oxygen interaction and the O-17 NMR interaction parameters. The O-17 CS shows greater sensitivity to the local alkali ions than that shown by the C-13 CS in the same compounds. It is found that the combination of metal ion-oxygen bond strength and cation size induce a deshielding shift up to similar to 70 ppm of O-17 delta(iso). The results also show the effects of different M-O interactions and C-O bond characteristics on the orientation of O-17 CS tensor components, and suggest that the O-17 quadrupolar parameters are systematically sensitive to the local cation environments around the carboxylate oxygen.
AB - O-17 NMR parameters, including chemical shift (CS) and electrical-field gradient (EFG) tensors, are calculated for oxalate compounds containing various different alkali ions using a DFT infinite periodic solid approach. This DFT study allows correlations to be found between the metal ion and oxygen interaction and the O-17 NMR interaction parameters. The O-17 CS shows greater sensitivity to the local alkali ions than that shown by the C-13 CS in the same compounds. It is found that the combination of metal ion-oxygen bond strength and cation size induce a deshielding shift up to similar to 70 ppm of O-17 delta(iso). The results also show the effects of different M-O interactions and C-O bond characteristics on the orientation of O-17 CS tensor components, and suggest that the O-17 quadrupolar parameters are systematically sensitive to the local cation environments around the carboxylate oxygen.
KW - metal ion-oxygen interactions, oxalates, O-17 NMR, chemical anisotropy shifts, electrical-field gradients, DFT calculations
U2 - 10.1016/j.chemphys.2007.07.007
DO - 10.1016/j.chemphys.2007.07.007
M3 - Journal article
VL - 337
SP - 144
EP - 150
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-3
ER -