Abstract
29Si NMR shieldings have been calculated by ab initio coupled Hartree-Fock perturbation theory for the orthosilicate species Si(OH)4, Si(OH)3O-, Si(OH)2O 2-2 , Si(OH)O 3-3 and SiO 4-4 using energy optimized geometries from ab initio Hartree-Fock calculations. The shielding of Si(OH)3O- is smaller than that of Si(OH)4 by 2.7 ppm and the shielding trend along the Si(OH)4 to SiO 4-4 series is decidedly nonlinear. The unprotonated O in Si(OH)3O- is more shielded and has a much smaller electric field gradient than do the protonated oxygens. Calculated anisotropies show the largest components of the shielding to lie along or near the short Si-O bonds. Calculations employing point charges in place of H reproduce the shielding trends in T d and S 4 symmetry Si(OH)4 semiquantitatively. The calculated trends in shielding with < Si-O-H can also be correlated with the energies of the Si3p,O2p σ bonding orbitals.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bakke AA, Chen H-W, Jolly WL (1980) A table of absolute coreelectron binding energies for gaseous atoms and molecules, J Electron Spectrosc Relat Phenom 20:333–366
Bodeur S, Millie P, Nenner I (1990) Single-and multiple-electron effects in the Sils photoabsorption spectra of SiX4 (X = H, D, F, Cl, Br, CH3, C2H5, OCH3, OC2H5) molecules; experiment and theory, Phys Rev A41:252–263
Buckingham AD (1960) Chemical shifts in the nuclear magnetic resonance spectra of molecules containing polar groups. Can J Chem 38:300–307
Chakoumakous BC, Gibbs GV (1986) Theoretical molecular orbital study of silanol-water interactions, J Phys Chem 90:996–998
Clark AH, Beagley B, Cruickshank DWJ, Hewitt TG (1970) An electron-diffraction investigation of gaseous perchloric acid and calculation of its skeletal force field and amplitudes of vibration, J Chem Soc A 1613–1616
Clark T (1984) Condensed phase radical anions, Faraday Discuss Chem Soc 78:203–212
Clark T, Chandrasekhar J, Spitznagel GW, Schleyer PVR (1983) Efficient diffuse-function augmented basis sets for anion calculations III. The 3–21 + G basis set for first-row elements, Li-F. J Comput Chem 4:294–301
Engelhardt VG, Zeigan D, Jancke H, Hoebbel D, Wieker W (1975) Zur Abhängigkeit der Struktur der Silicatanionen in wässrigen Natriumsilicatlösungen vom Na: Si-Verhältnis Zeit. Anorg Allg Chem 418:17–28
Fleischer U, Schindler M, Kutzelnigg W (1987) Magnetic properties in terms of localized quantities. VI. Small hydrides, fluorides and homonuclear molecules of phosphorus and silicon, J Chem Phys 86:6337–6347
Flygare WH, Goodisman J (1968) Calculation of diamagnetic shielding in molecules, J Chem Phys 49:3122–3125
Gianolio L, Pavani R, Clementi E (1978) A new algorithon for obtaining contracted basis sets from Gaussian type functions, Gazz Chim Ital 108:181–205
Grimmer AR (1985) Correlation between individual Si-O bond lengths and the principal values of the 29Si chemical shift tensor in solid silicates, Chem Phys Lett 119:416–420
Hansen AE, Bouman TD (1985) Localized orbital/local origin method for calculation and analysis of NMR shieldings. Application to 13C shieldings tensor, J Chem Phys 82:5035–5047
Harris RK, Newman RH (1977) 29Si NMR studies of aqueous silicate solutions, J Chem Soc Faraday Trans II 73:1204–1215
Harris RK, Knight CTG, Hull WE (1981) Nature of species present in an aqueous solution of potassium silicate, J Am Chem Soc 103:1577–1578
Hehre WJ, Radom L, von R. Schleyer P, Pople JA (1986) Ab Initio Molecular Orbital Theory, Wiley New York
Hess AC, McMillan PF, O'Keeffe M (1986) Force fields for SiF4 and H4SiO4. Ab initio molecular orbital calculations, J Phys Chem 90:5661–5665
Hess AC, McMillan PF, O'Keeffe M (1987) Ab initio force field of the S4 conformation of H4SiO4, J Phys Chem 91:1395–1396
Jamieson PB, Dent Glasser LS (1966) Sodium silicate hydrates. II. The crystal structure of Na2O ·SiO2 ·9H2O, Acta Crystallogr 20:688–693
Knight CTG (1988) A two-dimensional silicon-29 nuclear magnetic resonance spectroscopic study of the silicate anions present in an aqueous potassium silicate, J Chem Soc Dalton Trans 1457–1462
Koffman DM, Moll SH (1966) The effect of chemical combination on the K x-ray spectra of silicon, Adv X-ray Anal 9:323–328
Koppel I, Pikver R, Sugis A, Suurmaa E, Lippma E (1981) FT ICR study of the structure and solvent effects on basicity of some anions in gas phase, Org React 18:3–18
Lipscomb WN (1966) The chemical shift and other second-order magnetic and electric properties of small molecules, Adv Magn Res 2:137–224
O'Keeffe M, Domenges B, Gibbs GV (1985) Ab initio molecular orbital calculations on phosphates: comparison with silicates, J Phys Chem 89:2304–2309
Schaefer III HF, Klemm RA, Harris FE (1968) Atomic hyperfine structure. I. Polarization wave functions for the ground states of B, C, N, O and F, Phys Rev 176:49–58
Schmidt MW, Boatz JA, Baldrige KK, Kosek S, Gordon MS, Elbert ST, Lam B (1987) GAMESS. QCPE Bull 7:115
Schwarz WHE (1975) Interpretation of the core electron excitation spectra of hydride molecules and the properties of hydride radicals, Chem Phys 11:217–228
Sjoberg S, Ohman LO, Ingri N (1985) Equilibrium and structural studies of silicon (IV) and aluminum (III) in aqueous solution II > Polysilicate formation in alkaline aqueous solutions. A combined potentiometric and 29Si NMR study, Acta Chem Scand A 39:93–107
Sternberg V (1988) Theory of the influence of the second co-ordination sphere on the chemical shift, Mol Phys 63:249–267
Tossell JA (1975) The electronic structures of Si, Al and Mg in tetrahedral coordination with oxygen from SCF Xα MO calculations, J Am Chem Soc 97:4840–4844
Tossell JA (1981) Structures and cohesive properties of hydroxides and fluorides calculated using the modified electron gas ionic model, Phys Chem Minerals 7:15–19
Tossell JA (1984) Correlation of 29Si nuclear magnetic resonance chemical shifts in silicates with orbital energy differences obtained from x-ray spectra, Phys Chem Mineral 10:137–141
Tossell JA (1990) Ab initio calculation of the structures, Raman frequencies in Zn NMR spectra of tetrahedral complexes of Zn2+, Chem Phys Lett 169:145–149
Tossell JA, Lazzeretti P (1986) Ab initio calculation of 29Si NMR chemical shifts for some gas phase and solid state silicon fluorides and oxides, J Chem Phys 84:369–374
Tossell JA, Lazzeretti P (1987a) Ab initio calculation of the 31P shielding tensor for the series 660–01 660–02 and for HPO 2-4 , Chem Phys Lett 140:37–40
Tossell JA, Lazzeretti P (1987b) Ab initio calculations of oxygen nuclear quadrupole coupling constants and oxygen and silicon NMR shielding constants in molecules containing Si-O bonds, Chem Phys 112:205–212
Tossell JA, Lazzeretti P (1988) Calculation of NMR parameters for bridging oxygen in H3T-O-T'H3 linkages (T, T′ = Al, S, P), for oxygen in SiH3O-, SiH3OH and SiH3OMg+ and for bridging fluorine in H3SiFSiH +3 , Phys Chem Minerals 15:564–569
Ugliengo P, Saunders V, Garrone E (1990) Silanol as a model for the free hydroxyls of amorphous silica: Ab initio calculation of the interaction with water, J Phys Chem 94:2260–2267
Van Duijneveldt FG (1971) Gaussian basis sets for the atoms H-Ne for use in molecular calculations, IBM Res Rept RJ 945
Walter TH, Turner GL, Oldfield E (1988) Oxygen-17 cross-polarization NMR spectroscopy of inorganic solids, J Magnet Res 76:106–120
Wan H-X, Moore JH, Tossell JA (1989) Electron scattering cross sections and negative ion states of siliane and halide derivatives of silane, J Chem Phys 91:7340–7347
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tossell, J.A. Calculation of the effect of deprotonation on the Si NMR shielding for the series Si(OH)4 to SiO 4−4 . Phys Chem Minerals 17, 654–660 (1991). https://doi.org/10.1007/BF00203846
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00203846