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Temperature dependence of IR absorption of hydrous/hydroxyl species in minerals and synthetic materials

¹ Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, U.K.
² National Laboratory of Crystal Material, Institute of Crystal Material, Shandong University, Jinan 250100, Shandong, P.R. China
³ Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia, V6T 1Z4, Canada
⁴ Department of Geography and Geosciences, University of Louisville, Louisville, Kentucky, U.S.A.
⁵ College of Materials and Chemistry and Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, P.R. China
⁶ Institut für Mineralogie und Kristallographie, Universität Wien—Geozentrum, Althanstrasse 14, A-1090 Wien, Austria
⁷ Mineralogisch-Petrographisches Institut, Universität Hamburg, Grindelallee 48, D-20146 Hamburg, Germany

Correspondence: ^* E-mail: mz10001{at}esc.cam.ac.uk

We report on temperature dependencies of infrared (IR) fundamental, combination, and overtone vibrations of hydroxyl species (OH) in nominally anhydrous minerals (e.g., titanite), ferroelectric crystals (KTa_1–xNb_xO₃, KTN), layer silicates (talc, mica, and pyrophyllite), and hydrous minerals such as apatite and synthetic hydrous/deuterated garnets [Ca₃Al₂(O₄H₄)₃ and Ca₃Al₂(O₄D₄)₃] for the temperature range of 20–300 K. Data obtained by high-resolution FTIR spectroscopy show that increasing temperature generally leads to a decrease in the band height and band area of fundamental vibrations of hydroxyl species, whereas the combination and first-overtone bands commonly show different temperature dependencies. The results show that in the investigated temperature range, the variations of the band height and area for different OH bands (especially for combinations and overtones) on cooling or heating do not reflect changes in OH concentrations in the materials, but relate to temperature-dependent absorption coefficients. The observations imply that absorption coefficients calibrated at room temperature cannot necessarily be used for the determination of hydroxyl contents at other temperatures.

Key Words: Infrared spectroscopy • low temperature • apatite • hydrous garnet • pyrophyllite • talc • sericite • titanite

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