Abstract
NMR has become a very powerful technique for the characterization of the local order present in amorphous solids, glasses and aqueous solutions. The NMR shielding constant depends upon the identity, number and distance(s) of nearest-neighbour atoms, upon the nature of the connection(s) between the nearest neighbour units and upon the identities, distances and angular relationships of the atoms in the second nearest-neighbour coordination sphere. Ab initio SCF calculations on carefully chosen molecular clusters have reproduced many of the trends in shielding constants observed in molecules and solids. For species for which no appropriate crystalline models exist, ab initio techniques have been used to calculate equilibrium structures and NMR shieldings have then been calculated at those structures, to assist in species identification. Changes in shielding constants have been correlated with changes in other electronic properties, so as to give a unified picture of the electronic structure of the species. Our calculations on O, Al, Si, P, Zn and Cd NMR shieldings, using both conventional common-origin coupled Hartree-Fock theory and the localized-orbital local-origin modification known as LORG, have reproduced many trends in both isotropic and anisotropic NMR shielding values and have, in some cases, substantiated qualitative interpretations of shielding trends. As examples of geochemical applications of such calculations, we consider the variation of Si NMR shieldings and O electric field gradients with <Si-O-Si in siloxanes and silicates, the change in Si shielding with coordination number, the anisotropy of the 29Si NMR shielding tensor in olivine (Mg2SiO4), Al NMR shieldings and electric field gradients for various Al fluorides and oxyfluorides in F-bearing aluminosilicate glasses, and Zn and Cd NMR shieldings for chlorides and bisulfides in aqueous solution. Erroneously large predicted values of O shieldings from conventional CHF theory are corrected by the LORG approach or by a simple core electron correction, while highly polar compounds, such as the Al fluorides, are shown to present problems for LORG in its conventional implementation. Our results emphasize the need for simultaneous study of other properties which complement the NMR results, for improvements in methodology and computer capabilites which will allow the study of more realistic model systems or real bulk solids and for further study of the relationship between NMR shielding constants and other electronic properties.
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References
Ackerman, J. J. H., Orr. T. V., Bartuska, V. J. and Maciel, G. E. (1979), Effect of halide complexation of Cadmium (II) on Cadmium-113 chemical shifts, J. Am. Chem. Soc., 101, 341–347
Brinker, C. J., Brow, R. K., Tallant, D.R. and Kirkpatrick, R. J. (1990) Surface structure and chemisty of high surface area silica gels, J. Noncrystal. Solids, 120, 26–33
Butterworth, P., Hillier, I.H., Burton, N.A., Vaughan, D.J., Guest, M.F. and Tossell., J.A. (1992), Calculations of the structures, stabilities, Raman spectra and NMR spectra of CdCln(OH2)a2−n, CdBrn(OH2)a2−n and ZnCln(OH2)a2−n species in aqueous solution, submitted to J. Phys
Engelhardt,G. and Radeglia, R. (1984), A semi-empirical quantum-chemical rationalization of the correlation between SiOSi angles and 29Si NMR chemical shifts of silica polymorphs and framework aluminosilicates (zeolites), Chem. Phys. Lett., 108, 271–274
Farnan, I., Grandinetti, P.J., Baltisberger, J. H., Stebbins, J. F., Werner, U., Eastman, M. A. and Pines, A. (1992), Quantification of the disorder in network-modified silicate glasses, Nature, 358, 31–35
Flygare, W.H. and Goodisman, J. (1968), Calculation of diamagnetic shielding in molecules, J. Chem. Phys., 49, 3122–3125
Gibbs, G.V. (1982), Molecules as models for bonding in silicates, Amer. Mineral., 67, 421–450
Hansen, A.E. and Bouman, T.D. (1985), Localized orbital local origin method for calculation and analysis of NMR shieldings, Applications to 13C shielding tensors, J. Chem. Phys., 82, 5033–5047
Jameson, C. J., deDios, A. and Jameson, A. K. (1990), Absolute shielding scale for 31P from gas-phase NMR studies, Chem. Phys. Lett., 167, 575–582
Kohn, S.C., Dupree, R., Mortuza, M.G. and Henderson, C.M.B. (1991), NMR evidence for five-and six-coordinated aluminum fluoride complexes in F-bearing aluminosilicate glasses, Amer. Mineral., 76, 309–312
Kruger, H., Lutz, O., Schwenk, A. and Stricker, G. (1974), Nuclear magnetic resonance studies of 111Cd, Z. Phys., 266, 233–237
Lasaga, A. C. and Gibbs, G. V. (1987), Applications of quantum mechanical potential surfaces to mineral physics calculations, Phys. Chem. Minerals, 14, 107–117
Lazzeretti, P. and Zanasi, R. (1980), Theoretical determination of the magnetic properties of HC1, H2S, PH3 and SiH4 molecules, J. Chem. Phys., 72, 6768–6776
Lindsay, C.G. and Tossell, J.A. (1991), Ab initio calculations of 17O and nT NMR parameters (nT=31p,29Si) in H3TOTH3 dimers and T309 trimeric rings, Phys. Chem. Minerals, 18, 191–198
Lippmaa, E., Magi, N., Samoson, S., Engelhardt, G. and Grimmer, A.-R. (1980), Structural studes of silicates by solid-state high-resolution 29Si NMR, J. Am. Chem. Soc., 102, 4889–4893
Lipscomb, W. N. (1966), The chemical shift and other second-order magnetic and electric properties of small molecules, pp. 137–176 in Advances in Magnetic Resonance, Vol. 2, ed. J. S. Waugh
Maciel, G. E., Simeral, L. and Ackerman, J. J. H. (1977), Effect of complexation of Zn(II) on Zinc-67 chemical shifts, J. Phys. Chem. 81, 263–267
Malkin, V.G. and Zhidomirov, G.M. (1990), Quantum-chemical calculations of 29Si chemical shifts in zeolites, Zeolites, 10, 207–209
McKillop, K.L., Gillette, G.R., Powell, D.R. and West, R. (1992), 1,2-Disiladioxetanes: structure, rearrangement, and reactivity, J. Am. Chem. Soc., 114, 5203–5208
Marsmann, H. (1981), 29Si-NMR spectroscopic results, pp. 65–235 in NMR Basic Principles and Progress, Vol. 17, Oxygen-17 and Silicon-29, ed. Diehl, P., Ruck, E. and Kosfeld, R.
Nakatsuji, H., Kanda, K., Endo, K. and Yonezawa, T. (1984) Theoretical study of the metal chemical shift in nuclear magnetic resonance. Ag, Cd, Cu and Zn complexes, J. Am. Chem. Soc, 106, 4653–4660
Pisani, C. (1987) Hartree-Fock ab initio approaches to the solution of some solid-state problems: state of the art and prospects, Int. Rev. Phys. Chem., 6, 367–384
Radeglia, R. and Engelhardt, G. (1985), Correlation of Si-O-T (T=Si or Al) angles and 29Si NMR chemical shifts in silicates and aluminosilicates. Interpretation by semi-empirical quantum-chemical considerations, Chem. Phys. Lett., 114, 28–30
Santos, R. A., Gruff, E. S., Koch, S. A. and Harbison, G. S. (1991), Solid-state 19Hg and 113Cd NMR studies of mercury and cadmium thiolate complexes. Spectroscopic models for [Hg(SCys)n] centers in the bacterial mercury resistance proteins, J. Am. Chem. Soc., 113, 469–475
Sauer, J. (1989), Molecular models in ab initio studies of solids and surrfaces: from ionic crystals and semiconductors to catalysts, Chem. Rev. 89, 199–255
Skibsted, J., Hjorth, J. and Jakobsen, H. J. (1990), Correlation between 29Si NMR chemical shifts and mean Si-O bond lengths for calcium silicates, Chem. Phys. Lett., 172, 279–283
Smith, J. V. and Blackwell, C.S. (1983), Nuclear magnetic resonance of silica polymorphs, Nature, 303, 223–225
Thomas, J. M., Klinowski, J., Ramdas, S., Huner, B.K. and Tennakoon, D.T.B. (1983), The evaluation of non-equivalent tetrahedral sites from 29Si NMR chemical shifts in zeolites and related aluminosilicates, Chem. Phys. Lett., 102, 158–162
Tossell, J.A. (1977), A comparison of silicon-oxygen bonding in quartz and magnesian olivine from X-ray spectra and molecular orbital calculations, Amer. Mineral. 62, 136–141
Tossell, J.A. (1984), Correlation of 29Si nuclear magnetic resonance chemical shifts in silicates with orbital energy differences obtained from X-ray spectra, Phys. Chem. Minerals, 10, 137–141
Tossell, J.A. (1990a), Calculation of NMR shieldings and other properties for three and five coordinate Si, three coordinate o and some siloxane and boroxol ring compounds, J. Noncrystal. Solids, 120, 13–19
Tossell, J.A. (1990b),Ab initio calculation of the structures, Raman frequences and Zn NMR spectra of tetrahedral complexes of Zn2+, Chem. Phys. Lett., 169, 145–149
Tossell, J.A. (1991a), Calculation of the effect of deprotonation on the Si NMR shielding for the series Si(OH)4 to SiO4−4, Phys. Chem. Minerals, 17, 654–660
Tossell, J. A. (1991b), Calculation of the structures, stabilities, and Raman and Zn NMR spectra of ZnCln(OH2)a2−n species in aqueous solution, J. Phys. Chem., 95, 366–371
Tossell, J. A. (1992a), Theoretical studies of the speciation of Al in F-bearing aluminosilicate glasses, Amer Mineral., in press
Tossell, J.A. (1992b), Calculation of the 29Si NMR shielding tensor in forsterite, Phys. Chem. Minerals, in press
Tossell, J. A. and Lazzeretti, P. (1986), Ab initio calculations of 29Si NMR chemical shifts for some gas phase and solid state silicon fluorides and oxides, J. Chem. Phys., 84, 369–374
Tossell, J. A. and Lazzeretti, P. (1987), Ab initio calculation of the 31P NMR shielding tensor for the series POaFb−(2a+b−5), a+b=4 and for HPO4−2, Chem. Phys. Lett., 140, 37–40
Tossell, J. A. and Lazzeretti, P. (1988), Calculation of NMR parameters for briding oxygens in H3T-O-TH3 linkages (T,T=A1, Si,P), for oxygen in SiH3O− ,SiH3OH and SiH3OMg+ and for bridging fluorine in H3SiFSiH3 +, Phys. Chem. Minerals, 15, 564–569
Tossell, J. A. and Vaughan, D.J. (1992), Bisulfide complexes of Zn and Cd in aqueous solution: calculation of structure, stability, vibrational and NMR spectra and of speciation on sulfide mineral surfaces, submitted to Geochim Cosmochim. Acta
Weiden, N. and Rager, H. (1985), The chemical shift of the 29Si nuclear magnetic resonance in a synthetic single crystal of Mg2SiO4, Z. Naturforsch., 40a, 126–130
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Tossell, J.A. (1993). Applications of NMR Shielding Constant Calculations in Mineralogy and Geochemistry. In: Tossell, J.A. (eds) Nuclear Magnetic Shieldings and Molecular Structure. NATO ASI Series, vol 386. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1652-7_14
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DOI: https://doi.org/10.1007/978-94-011-1652-7_14
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