Yoshiasa Akira, Nakatsuka Akihiko, Okube Maki, Katsura Tomoo
Graduate School of Science and Technology, Kumamoto University, Kumamoto 860-8555, Japan.
Acta Crystallogr B Struct Sci Cryst Eng Mater. 2013 Dec;69(Pt 6):541-6. doi: 10.1107/S2052519213028248. Epub 2013 Nov 18.
The high-temperature clinoenstatite (HT-CEn) is one of the most important MgSiO3 pyroxene polymorphs, but the details of its structure and stability have been uncertain. The single crystal of the C2/c HT-CEn end-member is firstly synthesized by rapid pressure-temperature quenching from 15-16 GPa and 1173-2173 K. The single-crystal X-ray diffraction analysis shows unusual bonding distances and static disorder of the atoms frozen in this metastable structure. The degree of kinking of the silicate tetrahedral chains is 175° for HT-CEn. The chain angle for HP-CEn is substantially smaller (135°), but the angle for L-CEn is in the opposite direction at -160° (= 200°). The degree of kinking increases by being curved by more than 180° for the transition from HT-CEn to L-CEn. As for the reverse change from the expansion to the stretch, a potential barrier exists at the point of the continuity. It is suggested that the reason why a structure can be quenched under ambient conditions is as follows: the present HT-CEn single crystal has been formed by the isosymmetric phase transition from the high-pressure C2/c clinoenstatite (HP-CEn). The presence of HT-CEn from HP-CEn in natural rocks is an indicator of quenching history, which leads to the possibility that it exists in shocked meteorites and impact materials.
高温斜顽辉石(HT-CEn)是最重要的MgSiO₃辉石多晶型物之一,但其结构和稳定性的细节尚不确定。通过在15 - 16吉帕和1173 - 2173 K下快速压力-温度淬火,首次合成了C2/c HT-CEn端元的单晶。单晶X射线衍射分析表明,在这种亚稳结构中存在异常的键长和原子的静态无序。HT-CEn的硅酸盐四面体链的扭折程度为175°。高压斜顽辉石(HP-CEn)的链角明显更小(135°),但低温斜顽辉石(L-CEn)的角度在相反方向为-160°(= 200°)。从HT-CEn到L-CEn的转变中,扭折程度通过超过180°的弯曲而增加。至于从膨胀到拉伸的反向变化,在连续性点存在势垒。有人认为结构能够在环境条件下淬火的原因如下:目前的HT-CEn单晶是由高压C2/c斜顽辉石(HP-CEn)通过等对称相变形成的。天然岩石中HP-CEn产生的HT-CEn是淬火历史的一个指标,这导致它存在于冲击陨石和撞击物质中的可能性。