Original paper

Proton disorder in dehydrated hemimorphite – IR spectroscopy and X-ray structure refinement at low and ambient temperatures

Libowitzky, Eugen; Kohler, Thomas; Armbruster, Thomas; Rossman, George R.

European Journal of Mineralogy Volume 9 Number 4 (1997), p. 803 - 810

14 references

published: Jul 23, 1997
manuscript accepted: Jan 13, 1997
manuscript received: Jul 12, 1996

DOI: 10.1127/ejm/9/4/0803

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Abstract

Abstract Polarized IR absorption spectra of dehydrated hemimorphite single-crystals [Zn4Si2O7(OH)2] were recorded between 82 and 373 K. The crystal structure, including the proton positions, was refined in space group Imm2 from single-crystal X-ray data measured at 110 and 298 K. Both methods, as well as electrostatic and crystal chemical considerations, show that the protons of the hydroxide groups are disordered in the structural channels. One proton is located at the line between two O3 atoms (03-03' = 2.99-3.02 Å) thus building up a weak H bond. The corresponding O-H stretching band occurs at -3530 cm-1 and is polarized parallel to a. Due to proton-proton repulsion, the O-H vector of the other H atom deviates from the 03-03' line. As a consequence, the corresponding IR stretching vibration is observed at -3600 cm-1 and components of this band occur parallel to a and c. The disorder is also reflected by the large anisotropic displacement parameter U33 of the O3 atom. To test for a possible low-temperature phase transition (similar to that in natural hemimorphite), birefringence values were determined in (010) and (001) sections between 83 and 373 K. However, the smooth curves do not indicate a transition. This is explained by the lack of an additional proton acceptor (05 of the water molecule in hemimorphite) in the dehydrated phase.

Keywords

dehydrated hemimorphiteinfrared spectroscopycrystal structureproton disorde