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To obtain a better understanding of the structure of kaolin-group minerals, infrared spectra of structural OH in 1:1 dioctahedral clays were recorded as a function of temperature between 300 and 5 K. The low- and high-frequency components of the absorption bands of the structural OH groups shifted in opposite directions as the temperature changed and gave better resolution of the spectra. This behavior with temperature was used as a basis for assigning the stretching and bending modes of structural OH in the studied clays. Dichroic components, which are the result of coupling phenomena, were found at 3692, 3650, and 3644 cm-1 for kaolinite, dickite, and nacrite, respectively, and were attributed to vibrations of inner-surface OH groups which are, even in kaolinite, all nearly perpendicular to the sheet. The frequency and behavior with temperature of the corresponding decoupled OD groups indicate that inner-surface hydroxyls are involved in stronger hydrogen bonds in dickite than in kaolinite.

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