title: Second-degree twinning and dynamic disorder in the crystal structure of deca-dodecasil 3R.
abstract: The structure of deca-dodecasil 3R (DD-3R), Si120O240, a very well suited material for the synthesis of inorganic/organic composites structured on a nanometer level, has been investigated in detail. So far, a highly complicated twinning has hampered its structure description at a desirable level of accuracy. This twinning has now been resolved and a new structure determination is presented. Structure refinement in the R\bar 3 space group revealed a large, unusually shaped atomic displacement ellipsoid for oxygen-bridging units (tetrahedra), bridging Si-O bonds shorter than expected and the linear Si-O-Si' bond angle dictated by special positions at a threefold axis. A structure model based on a statistically disordered bridging O atom improved the accuracy of the Si-O bonds of interest, but provided unacceptable O-O contacts. To solve this dilemma, ab initio NVT molecular dynamics calculations were performed to study the possible configurations. Wavelet analysis of the time variations of selected Si-O distances pointed to a synchronous shift of the whole building units (tetrahedra). Low-frequency features of the calculated phonon density of states agree well with the published INS (inelastic neutron scattering) spectra of several silica polymorphs, indicating that the nature of the disorder in DD-3R is dynamic rather than static.
authors.affiliation: Department of Chemical and Biological Engineering, Division of Materials and Surface Chemistry, Subdivision of Inorganic Environmental Chemistry, Chalmers University of Technology, SE-412 96 Göteborg, Sweden.
authors.forename: Vratislav
authors.initials: V
authors.lastname: Langer
authors.forename: Lubomír
authors.initials: L
authors.lastname: Smrcok
authors.forename: Daniel
authors.initials: D
authors.lastname: Tunega
authors.forename: Gernot
authors.initials: G
authors.lastname: Wirnsberger