Greathouse Jeffery A, Allendorf Mark D
Geochemistry Department, Sandia National Laboratories, PO Box 5800, Albuquerque, New Mexico 87185, USA.
J Am Chem Soc. 2006 Aug 23;128(33):10678-9. doi: 10.1021/ja063506b.
Force field parameters for use with metal-organic framework-5 (MOF-5 or IRMOF-1) are presented. Flexibility within the framework is included in this model, so that structural changes upon interaction with adsorbate molecules can be observed and quantified. The model was validated by comparing simulated lattice parameters of pure MOF-5 with X-ray diffraction results. For the first time, molecular dynamics simulations have been performed that show how water interacts with MOF-5. The framework is stable at water contents up to 2.3% by mass, but distortion in the lattice structure is already evident. At water contents of 3.9% and higher, the framework collapses because of the replacement of MOF O atoms by water O atoms in the Zn coordination shells. As a result, inorganic MOF O atoms are no longer coordinated by four Zn ions, and benzene dicarboxylate linkers are no longer tethered to Zn centers.
本文给出了用于金属有机骨架-5（MOF-5或IRMOF-1）的力场参数。该模型考虑了骨架内部的柔性，从而能够观察并量化与吸附质分子相互作用时的结构变化。通过将纯MOF-5的模拟晶格参数与X射线衍射结果进行比较，对该模型进行了验证。首次进行了分子动力学模拟，展示了水与MOF-5的相互作用方式。在水含量高达2.3%（质量）时，骨架是稳定的，但晶格结构的畸变已经很明显。在水含量为3.9%及更高时，由于锌配位壳层中的MOF氧原子被水分子氧原子取代，骨架发生坍塌。结果，无机MOF氧原子不再由四个锌离子配位，苯二甲酸酯连接体也不再与锌中心相连。
