Liu Zheng, Terasaki Osamu, Ohsuna Tetsu, Hiraga Kenji, Camblor Miguel A, Díaz-Cabañas Maria-José, Cheetham Anthony K
CREST, JST, Department of Physics, Graduate School of Science Tohoku University, Sendai 980-8578, (Japan).
Chemistry. 2002 Oct 4;8(19):4549-56. doi: 10.1002/1521-3765(20021004)8:19<4549::AID-CHEM4549>3.0.CO;2-Z.
A detailed investigation of the structure of microporous silica, SSZ-24, is presented. It is shown by X-ray powder diffraction and (29)Si MAS NMR experiments that the structure deviates from the previously proposed AlPO(4)-5-type structure. At room temperature, electron diffraction (ED) patterns exhibit extra diffraction spots, which can be attributed to an incommensurate structural modulation along the c axis. This in turn results in a pleat pattern in real space with two different intervals arranged aperiodically along the c axis, as observed with high-resolution electron microscopy (HREM). The modulated structure may easily turn into a disordered one through excessive electron irradiation or heat-treatment. In order to understand the origin of the modulation, soft phonon-modes of the ideal premodulated structure were analyzed by the use of the rigid-unit-mode model. The distribution of soft modes in reciprocal space might correspond roughly to diffuse streaks that could be observed in the diffraction patterns at higher temperatures. It was found that several phonon branches soften at specific wave vectors, which are incommensurate with respect to the original period and might be responsible for the modulation. We present a simple analytic treatment to deduce the wave vectors and associated displacement eigenvectors for the incommensurate soft-modes.
本文对微孔二氧化硅SSZ-24的结构进行了详细研究。X射线粉末衍射和(29)Si MAS NMR实验表明,该结构与先前提出的AlPO(4)-5型结构不同。在室温下,电子衍射(ED)图案显示出额外的衍射斑点,这可归因于沿c轴的非公度结构调制。这进而导致在实空间中形成褶皱图案,其中两个不同的间距沿c轴非周期性排列,这与高分辨率电子显微镜(HREM)观察到的结果一致。通过过度电子辐照或热处理,调制结构可能很容易转变为无序结构。为了理解调制的起源,利用刚性单元模式模型分析了理想预调制结构的软声子模式。软模式在倒易空间中的分布可能大致对应于在较高温度下衍射图案中可观察到的漫散条纹。研究发现,几个声子分支在特定波矢处软化,这些波矢与原始周期非公度,可能是导致调制的原因。我们提出了一种简单的解析方法来推导非公度软模式的波矢和相关的位移本征矢量。