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Rietveld Refinement and Fourier-Transform Infrared Spectroscopic Study of the Dickite Structure at Low Temperature

Published online by Cambridge University Press:  28 February 2024

David L. Bish  and
Clifford T. Johnston
David L. Bish
Affiliation:
Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Clifford T. Johnston
Affiliation:
Department of Soil Science, 2169 McCarty Hall, University of Florida, Gainesville, Florida 32611
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Abstract

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The full structure of dickite from St. Claire, Pennsylvania, including hydrogen atoms, was refined in space group Cc using time-of-flight neutron powder diffraction data obtained at 12 K and Rietveld refinement/difference-Fourier methods (Rwp = 2.62%, reduced χ2 = 1.915, 113 variables, a = 5.1474(6)Å, b = 8.9386(10)Å, c = 14.390(2)Å, and ß = 96.483(1)°). The non-hydrogen structure is essentially identical to published structures for dickite, but the hydrogen positions are distinct. The inner hydroxyl group is approximately parallel to the (001) plane, inclined by 1.3° towards the tetrahedral sheet. Contrary to published low-temperature infrared (IR) spectra, there is no evidence that dickite possess lower symmetry at low temperatures although there is tentative evidence for statistical occupancy of H3 on more than one site. Low-temperature IR spectra of St. Claire and Wisconsin dickites do not show evidence for more than four hydroxyl groups and are consistent with the reported structure. Upon cooling from 300 to 15 K, the position of the OH3 stretching band increased from 3710 to 3731 cm−1. This large, positive shift in frequency was attributed to the increase in the internuclear O-H3 ⋯ O distance upon cooling. The frequency of the 3655 cm−1 band initially decreased by 2 cm−1 to 3653 cm−1 upon cooling from 300–125 K; however, the band increased in frequency by 1 cm−1 upon further cooling to 15 K. This unusual change in frequency upon cooling is consistent with the assignment of this band to OH2 and OH4. The position of the OH1 stretching band decreased from 3622 to 3620 cm−1 upon cooling, which was attributed, in part, to the observed increase in the Al-O(H1)-Al angle at low temperature.

Keywords

DickiteFTIRInfrared spectroscopyLow temperatureNeutron powder diffractionRietveld refinement
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 3 , June 1993 , pp. 297 - 304
Copyright
Copyright © 1993, The Clay Minerals Society

References

Adams, J. M. and Hewat, A. W., 1981 Hydrogen atom positions in dickite Clays & Clay Minerals 29 316 – 319 10.1346/CCMN.1981.0290410.CrossRefGoogle Scholar
Bellows, J. C. and Prasad, P. N., 1979 Dephasing times and linewidths of optical transitions in molecular crystals: Temperature dependence of line shapes, linewidths, and frequencies of Raman active phonons in naphthalene J. Chem. Phys. 70 1864 – 1871 10.1063/1.437664.CrossRefGoogle Scholar
Bish, D. L., 1989 Rietveld refinement of the kaolinite structure at 88, 294, and 573K Program and Abstracts, 26th Annual Meeting of the Clay Minerals Society 17.Google Scholar
Bish, D. L. and Von Dreele, R. B., 1990 The crystal structure of kaolinite including hydrogen atoms Program and Abstracts, 27th Annual Meeting of the Clay Minerals Society 25.Google Scholar
Bookin, A. S., Drits, V. A., Plancon, A. and Tchoubar, C., 1989 Stacking faults in kaolin-group minerals in the light of real structural features Clays & Clay Minerals 37 297 – 307 10.1346/CCMN.1989.0370402.CrossRefGoogle Scholar
Brindley, G. W., Kao, C.-C. Harrison, J L L M and Raythatha, R., 1986 Relation between structural disorder and other characteristics of kaolinites and dickites Clays & Clay Minerals 34 239 – 249 10.1346/CCMN.1986.0340303.CrossRefGoogle Scholar
Dollase, W. A., 1986 Correction of intensities for preferred orientation in powder diffractometry: Application of the March model J. Appl. Crystallogr. 19 267 – 272 10.1107/S0021889886089458.CrossRefGoogle Scholar
Farmer, V. C. and Farmer, V. C., 1974 The layer silicates The Infrared Spectra of Minerals London Mineralogical Society 331 – 363 10.1180/mono-4.15.CrossRefGoogle Scholar
Farmer, V. C. and Russell, J. D., 1964 The infra-red spectra of layer silicates Spectrochimica Acta 20 1149 – 1173 10.1016/0371-1951(64)80165-X.CrossRefGoogle Scholar
Gruner, J. W., 1932 The crystal structure of dickite Zeit. Krist. 83 394 – 404.Google Scholar
Johnston, C. T., Agnew, S. F. and Bish, D. L., 1990 Polarized single-crystal Fourier-transform infrared microscopy of Ouray dickite and Keokuk kaolinite Clays & Clay Minerals 38 373 – 583 10.1346/CCMN.1990.0380406.CrossRefGoogle Scholar
Joswig, W. and Drits, V. A., 1986 The orientation of the hydroxyl groups in dickite by X-ray diffraction N. Jb. Miner. Mh. 19 – 22.Google Scholar
Larson, A. C., and Von Dreele, R. B., (1988) Generalized structure analysis system: Los Alamos National Laboratory Rept. LAUR 86–748, 161 pp.Google Scholar
Newnham, R. E., 1961 A refinement of the dickite structure and some remarks on polymorphism in kaolin minerals Mineral. Mag. 32 683 – 704.Google Scholar
Newnham, R. E. and Brindley, G. W., 1956 The crystal structure of dickite Acta Crystallogr. 9 759 – 764 10.1107/S0365110X56002060.CrossRefGoogle Scholar
Pauling, L., 1930 The structure of the chlorites Proc. Natl. Acad. Sci, U.S.A. 16 578 – 582 10.1073/pnas.16.9.578.CrossRefGoogle ScholarPubMed
Prost, R., 1984 Etude par spectroscopic infrarouge a basse temperature des groupes OH de structure de la kaolinite, de la dickite et de la nacrite Agronomie 4 403 – 406 10.1051/agro:19840413.CrossRefGoogle Scholar
Prost, R., Dameme, A., Huard, E., Driard, J., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Infrared study of structural OH in kaolinite, dickite, and nacrite at 300 to 5 K Proc. Int. Clay Conf. Denver, 1985 Bloomington, Indiana The Clay Minerals Society 17 – 23.Google Scholar
Prost, R., Dameme, A., Huard, E., Driard, J. and Leydecker, J. P., 1989 Infrared study of structural OH in kaolinite, dickite, nacrite, and poorly crystalline kaolinite at 5 to 600 K Clays & Clay Minerals 37 464 – 468 10.1346/CCMN.1989.0370511.CrossRefGoogle Scholar
Rietveld, H. M., 1969 Profile refinement method for nuclear and magnetic structures J. Appl. Crystallogr. 2 65 – 71 10.1107/S0021889869006558.CrossRefGoogle Scholar
Rozhdestvenskaya, I. V., Bookin, A. S., Drits, V. A. and Finko, V. I., 1982 Proton positions and structural characteristics of dickite by X-ray diffraction Miner. Zhur. 4 52 – 58.Google Scholar
Sen Gupta, P. K., Schlemper, E. O., Johns, W. D. and Ross, F., 1984 Hydrogen positions in dickite Clays & Clay Minerals 32 483 – 485 10.1346/CCMN.1984.0320607.CrossRefGoogle Scholar
Scott, H. G., 1983 The estimation of standard deviations in powder diffraction Rietveld refinements J. Appl. Crystallogr. 16 159 – 163 10.1107/S0021889883010195.CrossRefGoogle Scholar
Von Dreele, R. B., Jorgensen, J. D. and Windsor, C. G., 1982 Rietveld refinement with spallation neutron powder diffraction data J. Appl. Crystallogr. 15 581 – 589 10.1107/S0021889882012722.CrossRefGoogle Scholar
Wilson, E. B. Jr. Decius, J. C. and Cross, P. C., 1955 Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra New York Dover Publications.Google Scholar