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Single-crystal IR spectroscopy of very strong hydrogen bonds in pectolite, NaCa_2[Si_3O_8(OH)], and serandite, NaMn_2[Si_3O_8(OH)]

Hammer, Vera M. F. and Libowitzky, Eugen and Rossman, George R. (1998) Single-crystal IR spectroscopy of very strong hydrogen bonds in pectolite, NaCa_2[Si_3O_8(OH)], and serandite, NaMn_2[Si_3O_8(OH)]. American Mineralogist, 83 (5-6). pp. 569-576. ISSN 0003-004X. http://resolver.caltech.edu/CaltechAUTHORS:20130502-084001635

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Abstract

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 Å that was found in previous X-ray structure refinements. At 1396 cm^(-1) (pectolite) and 1386 cm^(-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^(-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.


Item Type:Article
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http://ammin.geoscienceworld.org/content/83/5-6/569.abstractPublisherUNSPECIFIED
ORCID:
AuthorORCID
Rossman, George R.0000-0002-4571-6884
Additional Information:© 1998 Mineralogical Society of America. Manuscript received March 20, 1997. Manuscript accepted December 10, 1997. Paper handled by Hans Keppler. We thank C.T. Prewitt and M. Picard, Musée Canadien de la Nature, Ottawa, for the serandite and pectolite samples. Precession photographs were performed at the ETH Zürich. Preliminary IR measurements on pectolite were performed by R.D. Aines, Caltech. Editor A.M. Hofmeister and Associate Editor H. Keppler helped to improve the presentation and the transparency of the manuscript. E.L. is indebted to the Fonds zur Förderung der wissenschaftlichen Forschung, Austria for financial support during an Erwin-Schrödinger fellowship, project J01098-GEO, at the California Institute of Technology. G.R.R. acknowledges financial support from the National Science Foundation, grant EAR-9218980.
Funders:
Funding AgencyGrant Number
Fonds zur Förderung der wissenschaftlichen ForschungUNSPECIFIED
Erwin-Schrödinger Fellowship J01098-GEO
NSFEAR-9218980
Record Number:CaltechAUTHORS:20130502-084001635
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20130502-084001635
Official Citation: Vera M. F. Hammer, Eugen Libowitzky, and George R. Rossman 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)] American Mineralogist, June 1998, v. 83, p. 569-576
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:38227
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 May 2013 16:14
Last Modified:07 Feb 2017 03:52

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