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American Mineralogist; June 1998; v. 83; no. 5-6; p. 569-576
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Single-crystal IR spectroscopy of very strong hydrogen bonds in pectolite, NaCa 2 [Si 3 O 8 (OH)], and serandite, NaMn 2 [Si 3 O 8 (OH)]

Vera M. F. Hammer, Eugen Libowitzky, and George R. Rossman

Mineralogisch-Petrographische Abteilung, Naturhistorisches Museum, Wien, Austria
Universitaet Wien-Geozentrum, Austria
California Institute of Technology, United States

Polarized infrared absorption spectra of thin, oriented single-crystal slabs of pectolite and serandite were recorded between 4000 and 350 cm (super -1) at 298 and 83 K. The spectra of both minerals show a broad absorption region parallel to the silicate chains (b direction) that is centered around 1000 cm (super -1) , which is interrupted by a transmission window, and which is superimposed by sharp silicate, lattice, and overtone modes. This band is assigned to the OH stretching mode consistent with the alignment of the O-H . . . O hydrogen bond parallel to b and the short O . . . O distance of 2.45-2.48 Aa that was found in previous X-ray structure refinements. At 1396 cm (super -1) (pectolite) and 1386 cm (super -1) (serandite) an OH bending mode is observed in the IR spectra parallel to c. At low temperatures, this mode shifts up to higher frequencies (1403 cm (super -1) at 83 K in pectolite), whereas the down-shift of the OH stretching mode cannot be observed due to the extremely broad band width. The slightly higher energy of the bending mode in pectolite indicates a slightly stronger hydrogen bond with respect to serandite. However, the bond length in serandite is slightly shorter than that in pectolite. An asymmetric O-H . . . O bond is confirmed in pectolite and serandite through comparison with different materials with similar, very strong hydrogen bonds and low-energy OH stretching modes.

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