title: The influence of the long-range order on the vibrational spectra of structures based on sodalite cage.
abstract: Zeolites are a group of tecto-aluminosilicates with numerous practical applications, e.g. gas separators, molecular sieves and sorbents. The unique properties result from porous structure of channels and cages which are built from smaller units - the so-called Secondary Building Units (SBU), and sometimes also larger groups (Breck, 1974; Ciciszwili et al., 1974; Mozgawa, 2008; Čejka and van Bekkum, 2005). The aim of this study was the examination of the influence of long-range order on vibrational spectra of sodalite and zeolite A. Ab initio calculations (geometry optimizations and vibrational spectra calculations) of sodalite cage and selected SBU were carried out by means of Gaussian09 (Frisch et al., 2009) (in the case of isolated clusters) and Crystal09 (Dovesi et al., 2005, 2009) (for periodic structures). The obtained results were compared with the experimental spectra of sodalite and zeolite A crystal structures, synthesized under hydrothermal conditions. These results allowed analyzing of the long-range ordering influence on the vibrational spectra, as well as the identification of the characteristic vibrations in β cage based frameworks. It has been found, that based on small structural fragment (SBU) models a characteristic vibrations can be identify. However, full spectra analysis and especially the interpretation of far-infrared region of the spectra require using periodic models under the influence of translational crystal lattice.
authors.affiliation: Department of Silicate Chemistry and Macromolecular Compounds, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland. Electronic address: amikula@agh.edu.pl.
authors.forename: A
authors.initials: A
authors.lastname: Mikuła
authors.affiliation: Department of Silicate Chemistry and Macromolecular Compounds, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland.
authors.forename: M
authors.initials: M
authors.lastname: Król
authors.affiliation: Department of Silicate Chemistry and Macromolecular Compounds, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland.
authors.forename: A
authors.initials: A
authors.lastname: Koleżyński
mesh_terms: D008958:Models, Molecular; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D014732:Vibration; D017641:Zeolites / Q000737:chemistry*
chemical_list: D017641:Zeolites
keywords: Ab initio calculation; Sodalite; Vibrational spectra; Zeolite A; β cage