Abstract
Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO 4−4 cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Adams IM, Thomas JM, Bancroft GM (1972) An ESCA study of silicate minerals. Earth Planet Sci Lett 16:429–432
Adams IM, Evans S, Raid PI, Thomas JM, Walters MJ (1977) Quantitative analysis of aluminosilicates and other solids by x-ray photoelectron spectroscopy. Anal Chem 49:2001–2008
Brytov IA, Romashchenko YuN (1978) X-ray spectroscopic investigation of the electronic structure of silicon and aluminum oxides. Sov Phys Solid State 20:384–389
Brytov IA, Konashenol KI, Romashchenko YuN (1979) Crystallochemical effects on Al K and Si K emission and absorption spectra for silicate and aluminosilicate minerals. Geochem Intern 16:142–154
Dehmer JL (1972) Evidence of effective potential barriers in the x-ray absorption spectra of molecules. J Chem Phys 56:4496–4504
Dikov YuP, DEbolsky EI, Romashchenko YuN, Dolin SP, Levin AA (1977) Molecular orbitals of Si2 7/6−0 , Si3 10/8−0 , etc., and mixed (B, Al, P, Si) m applied to clusters and x-ray spectroscopy data of silicates. Phys Chem Minerals 1:27–41
Evans S, Raftery E (1980) Quantitative x-ray photoelectron diffraction studies of single-crystal silicates. Solid State Commun 33:1213–1215
Evans S, Adams JM, Thomas JM (1979) The surface structure and composition of layered silicate minerals: novel insight from x-ray photoelectron diffraction, K-emission spectroscopy and cognate techniques. Phil Trans R Soc Lond A292:563–591
Ferrett TA, Lindle DW, Heimann PA, Kerkhoff HG, Becker UE, Shirley DA (1986) Sulfur 1 s core-level photoionization of SF6. Phys Rev A 34:1916–1930
Grimmer AR, Fechner RP, Molgedey G (1981) High-resolution 29Si NMR in solid silicates, correlations between shielding tensor and Si-O bond length. Chem Phys Lett 77:331–335
Kinsey RA, Kirkpatrick RJ, Hower J, Smith KA, Oldfield E (1985) High resolution aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopic study of layer silicates, including clay minerals. Am Mineral 70:537–548
Kirkpatrick RJ (1988) MAS NMR spectroscopy of minerals and glasses. Reviews in Mineralogy 18:341–403
Klinowski J (1984) Nuclear magnetic resonance studies of zeolite. Progress in NMR spectroscopy 16:237–309
Kretz R (1983) Symbols for rock-forming minerals. Am Mineral 68:277–279
Li D, Bancroft GM, Kasrai M, Fleet ME, Feng XH, Tan KH, Yang BX (1993) High-resolution Si Kand L2,3-edge XANES of α-quartz and stishovite. Solid State Commun 87:613–617
Li D, Bancroft GM, Kasrai M, Fleet ME, Secco RA, Feng XH, Tan KH, Yang BX (1994a) X-ray absorption spectroscopy of silicon dioxide (SiO2) polymorphs: structural characterization of opal. Am Mineral 79:622–632
Li D, Bancroft GM, Kasrai M, Fleet ME, Feng XH, Tan KH (1994b) Silicon and phosphorus Kand L-edge XANES spectra of crystalline SiP2O7 and amorphous SiO2-P2O5. Am Mineral 79:785–788
Liebau F (1985) Structural Chemistry of Silicates: Structure, bonding and classification. Springer-Verlag, Berlin
Lippmaa E, Mägi M, Samoson A, Engelhardt G, Grimmer AR (1980) Structural studies of silicates by solid-state high-resolution 29Si NMR. J Am Chem Soc 102:4889–4893
Mägi M, Lippmaa E, Samoson A, Engelhardt G, Grimmer AR (1984) Solid-state high-resolution silicon-29 chemical shift in silicates. J Phys Chem 88:1518–1522
McComb DW, Brydson R, Hansen PL, Payne RS (1992) Qualitative interpretation of electron energy-loss near-edge structure in natural zircon. J Phys Condensed Matter 4:8363–8374
Nefedov VI, Yarzhemsky VG, Chuvaev AV, Trishkina EM (1988) Determination of effective atomic charge, extra-atomic relaxation and Madelung energy in chemical compounds in the bases of x-ray photoelectron and Auger transition energies. J Electron Spectrosc Reltd Phenom 46:381–404
Pitault B, Belin E, Boutouaba D, Senemaud C (1981) K x-ray emission spectra from natural silicates. Chem Phys Lett 81:123–126
Purton J, Urch DS (1989) High-resolution silicon 121–01 x-ray spectra and crystal structure. Mineral Mag 53:239–244
Seyama H, Soma M (1985) Bonding-state characterization of the constituent elements of silicate minerals by x-ray photoelectron spectroscopy. J Chem Soc, Faraday Trans I 81:485–495
Seyama H, Soma M (1987) Application of x-ray photoelectron spectroscopy to the study of silicate minerals. Research Report from the National Institute for Environmental Studies, Japan, No 111
Sherriff BL, Grundy HD (1988) Calculation of 29Si MAS NMR chemical shift from silicate mineral structure. Nature 332:819–822
Sherriff BL, Grundy HD, Hartman JS (1991) The relationship between 29Si MAS NMR chemical shift and silicate mineral structure. Eur J Mineral 3:751–768
Smith KA, Kirkpatrick RJ, Oldfield E, Henderson DM (1983) High-resolution silicon-29 nuclear magnetic resonance spectroscopic study of rock-forming silicates. Am Mineral 68:1206–1215
Tossell JA (1973) Molecular orbital interpretation of x-ray emission and ESCA spectral shifts in silicates. J Phys Chem Solids 34:307–319
Tossell JA (1975) The electronic structures of silicon, aluminum, and magnesium in tetrahedral coordination with oxygen from 121–02 calculation. J Am Chem Soc 97:4840–4844
Tossell JA, Gibbs GV (1977) Molecular orbital studies of geometries and spectral of minerals and inorganic compounds. Phys Chem Minerals 2:21–57
Urch DS, Murphy S (1974) The relationship between bond distance and orbital ionisation energies for a series of aluminosilicates. J Electron Spectrosc Relat Phenom 5:167–171
Urch DS (1989) Bonding in minerals: the application of PAX (Photoelectron and x-ray) spectroscopy to the direct determination of electronic structure. Mineral Mag 53:153–164
Wagner CD, Six HA, Jansen WT, Taylor JA (1981) Improving the accuracy of determination of line energies by ESCA: chemical state plots for silicon-aluminum compounds. Appl Surf Sci 9:203–213
Wagner CD, Passoja DE, Hillery HF, Kinisky TG, Six HA, Jansen WT, Taylor JA (1982) Auger and photoelectron line energy relationships in aluminum-oxygen and silicon-oxygen compounds. J Vac Sci Tech 21:933–944
Weiss CA, Altaner SP, Kirkpatrick RJ (1987) High-resolution 29Si NMR spectroscopy of 2:1 layer silicates: correlation among chemical shift, structure distortion, and chemical variations. Am Mineral 72:935–942
West RH, Castle JE (1982) The correlation of the Auger parameter with refractive index: an XPS study of silicates using Zr 122–03 radiation. Surf Interf Anal 4:68–75
Wiech G, Kurmaev EZ (1985) X-ray emission bands and electronic structure of crystalline and vitreous silica (SiO2). J Phys C, Solid State Phys 18:4393–3302
Yang BX, Middleton FH, Olssom BG, Bancroft GM, Chen JM, Sham TK, Tan KH, Wallace DJ (1992) Double-crystal monochromator beamline on the Aladdin 1-GeV storage ring. Rev Sci Instrum 63:1355–1358
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Li, D., Bancroft, G.M., Fleet, M.E. et al. Silicon K-edge XANES spectra of silicate minerals. Phys Chem Minerals 22, 115–122 (1995). https://doi.org/10.1007/BF00202471
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00202471