Abstract
Polarized IR spectra of planeparallel (0001) plates of synthetic smoky quartz, with E rotating around [0001], show that the absorption figures of OH− related absorption bands at 3380 (room temperature), 3365 and 3305 cm−1 (liquid nitrogen temperature, -196° C) are strongly anisotropic and violate the trigonal symmetry of low quartz. This effect is correlated with a non-uniform substitution of Si by Al on the three symmetrically equivalent Si sites, as revealed by EPR measurements. Random distribution of Al over the three Si sites, obtained by dry annealing of the samples in air, yields isotropic absorption figures in the (0001) plates. It is thus experimentally evident that the absorption bands at 3380, 3365 and 3305cm−1 are caused by the OH− stretching vibrations coupled with Al substituting for Si. For each experimentally determined integral absorption coefficient of the three absorption bands a theoretical absorption coefficient was calculated, based on the symmetry of low quartz and the given Al distribution. This was done for various orientations of the OH− dipoles with respect to the a axes of low quartz. By comparing the experimentally determined and calculated absorption coefficients, the orientation of the corresponding OH− dipoles with respect to the a axes could be determined.
Similar content being viewed by others
References
Aines RD, Rossman GR (1984) Water in minerals? A peak in the infrared. J Geophys Res 89:4059–4071
Aines RD, Kirby SH, Rossman GH (1984) Hydrogen Speciation in Synthetic Quartz. Phys Chem Minerals 11:204–212
Bambauer HU (1961) Spurenelementgehalte und γ-Farbzentren in Quarzen aus Zerklüften der Schweizer Alpen. Schweiz Mineral Petrogr Mitt 41:335–369
Barry TI, McNamara P, Moore WJ (1965) Paramagnetic Resonance and Optical properties of amethyst. J Chem Phys 42:2599–2606
Brown RN, Kahan A (1975) Optical absorption of irradiated quartz in the near I.R. J Phys. Chem Solids 36:467–476
Brunner G, Wondratschek H, Laves F (1961) Ultrarotuntersuchungen über den Einbau von H in natürlichem Quarz. Z Elektrochem, Ber Bunsenges Phys Chem 65:735–750
Bulka GR, Vinokurov VM, Nizamutdinov NM, Hasanova NM (1980) Dissymmetrization of Crystals: Theory and Experiment. Phys Chem Minerals 6:283–293
Chakraborty D, Lehmann G (1976) On the structures and orientations of hydrogen defects in natural and synthetic quartz crystals. Phys Status Solidi (a) 34:467–474
Cox RT (1976) ESR of an S = 2 centre in amethyst quartz and its possible identification as the d4 ion Fe4+. J Phys Chem, Solid State Phys 9:3355–3361
Dodd DM, Fraser DB (1965) The 3000–3900 cm−1 absorption bands and anelasticity in crystalline α-quartz. J Phys Chem Solids 26:673–686
Donnay JDH, LePage YL (1978) The Vicissitudes of the Low-Quartz Crystal Setting or the Pitfalls of Enantiomorphism. Acta Crystallogr A34:584–594
Geschwind S, Remeika J (1961) Paramagnetic Resonance of Gd3+ in Al2O3. Phys Rev 122:757–761
Griffiths JHE, Owen J, Ward IM (1954) Paramagnetic resonance in neutron-irradiated diamond and smoky quartz. Nature 173:439–442
Griffiths JHE, Owen J, Ward IM (1955) Magnetic resonance in irradiated diamond and quartz. Report of the Bristol Conference — Defects in Crystalline solids. Phys Soc Lond 81–87
Halliburton LE, Koumvakalis ME, Markes ME, Martin JJ (1981) Radiation effects in crystalline SiO2: The role of aluminium. J Appl Phys 52:3565–3574
Kats A (1962) Hydrogen in alpha-quartz. Philips Res Rep 17:133–195, 301–279
Krohmer P (1968) IR-Spektroskopie mit polarisiertem Licht. Analysentechnische Berichte 14
Kronenberg AK, Kirby SH, Aines RD, Rossman GR (1986) Solubility and diffusional uptake of hydrogen in quartz at high pressures: Implications for hydrolytic weakening. J Geophys Res 91:723–741
Lehmann G (1987) Defects in minerals. Cryst Lattice Defects 14:307–317
LePage Y, Donnay G (1976) Refinement of the Crystal Structure of Low-Quartz. Acta Crystallogr B32:2456–2459
Lipson HG, Kahan A (1985) Infrared characterization of aluminium and hydrogen defect centers in irradiated quartz. J Appl Phys 58:963–970
Mackey JH (1963) EPR study of impurity-related colour centers in Germanium-doped quartz. J Chem Phys 39:74–83
Mombourquette MJ, Weil JA (1985) Ab initio self-consistent-field molecular-orbital calculations on AlO4 centres in alpha-quartz. II. Can J Phys 63:1282–1293
Nuttall RHD, Weil JA (1981) The magnetic properties of the oxygen-hole aluminium centers in crystalline SiO2. I. [AlO4]∘. Can J Phys 59:1996–1708
O'Brien MCM (1955) The structure of the colour centres in smoky quartz. Proc R Soc A231:404–414
O'Brien MCM, Pryce MHL (1955) Paramagnetic resonance in irradialed diamond and quartz: Interpretation. Report of the Bristol Conference — Defects in Crystalline Solids. Phys Soc London 88–91
Pankrath R (1988) Spurenelementeinbau in Tief-Quarz als Funktion der Wachstumsbedingungen und Umprägungen unter trockenen und hydrothermalen Bedingungen. Dissertation Ruhr-Universität Bochum
Paterson MS (1982) The determination of hydroxyl by infrared absorption in quartz, silicate glasses and similar materials. Bull Mineral 105:20–29
Rumyantsev V, Novozhilov A (1980) Dependence on concentration of aluminium-centers and anomalous pleochroism on certain crystallization parameters in synthetic quartz. Sov Phys Crystallography 25:75–78
Schnadt R, Schneider J (1970) The electronic structure of the trapped hole center in smoky quartz. Phys Kondens Mater 11:19–42
Sibley WA, Martin JJ, Wintersgill MC, Brown JD (1979) The effect of irradiation on the OH− infrared absorption of quartz crystals. J Appl Phys 50:5449–5452
Siebers FB (1986) Inhomogene Verteilung von Verunreinigungen in gezüchteten und natürlichen Quarzen als Funktion der Wachstumsbedingungen und ihr Einfluß auf kristallphysikalische Eigenschaften. Dissertation Ruhr-Universität Bochum
Weil JA (1975) The aluminium centers in alpha-quartz. Rad Effects 25:261–265
Weil JA (1984) A Review of Electronic Spin Spectroscopy and Its Application to the Study of Paramagnetic Defects in Crystalline Quartz. Phys Chem Minerals 10:149–165
Wertz JE, Bolton JR (1972) Electron spin resonance. McGraw-Hill, New York
Wolfe R, Sturge MD, Merritt FR, VanUitert LG (1971) Faced-Related Site selectivity for Rare-Earth Ions in Yttrium Aluminium Garnet. Phys Rev Lett 26:1570
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Pankrath, R. Polarized IR spectra of synthetic smoky quartz. Phys Chem Minerals 17, 681–689 (1991). https://doi.org/10.1007/BF00202238
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00202238