Force-Field Development from Electronic Structure Calculations with Periodic Boundary Conditions: Applications to Gaseous Adsorption and Transport in Metal-Organic Frameworks
Force-Field Development from Electronic Structure Calculations with Periodic Boundary Conditions: Applications to Gaseous Adsorption and Transport in Metal-Organic Frameworks
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DOI：
10.1021/ct500094w
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发表时间：
2014-04-01
影响因子：
5.5
通讯作者：
Smit, Berend
中科院分区：
文献类型：
--
作者：
Lin, Li-Chiang;Lee, Kyuho;Smit, Berend
我们提出了一个系统的和有效的方法来获得准确的（nonpolarizable）力场周期性密度泛函理论（DFT）计算用于经典分子模拟。与其他传统方法相比，该方法需要减少计算成本。此外，整个过程是在一个完全周期系统中自洽进行的。通过使用这种方法得到的力场很好地预测了Mg-MOF-74内部的CO2和H2O吸附等温线，并且可以转移到Zn-MOF-74;通过将Mg-CO2相互作用替换为相应的Zn-CO2相互作用，我们获得了相应等温线的准确预测。我们已经应用这种方法来解决水对这些材料中烟气分离的影响。在一般情况下，CO2和H2O的混合物等温线计算与这些导出的力场显示出显着减少CO2的吸收与微量的水蒸气的存在。然而，发现水的影响在Mg-和Zn-M0 F-74之间定量地不同。
We present a systematic and efficient methodology to derive accurate (nonpolarizable) force fields from periodic density functional theory (DFT) calculations for use in classical molecular simulations. The methodology requires reduced computation cost compared with other conventional ways. Moreover, the whole process is performed self-consistently in a fully periodic system. The force fields derived by using this methodology nicely predict the CO2 and H2O adsorption isotherms inside Mg-MOF-74, and is transferable to Zn-MOF-74; by replacing the Mg-CO2 interactions with the corresponding Zn-CO2 interactions, we obtain an accurate prediction of the corresponding isotherm. We have applied this methodology to address the effect of water on the separation of flue gases in these materials. In general, the mixture isotherms of CO2 and H2O calculated with these derived force fields show a significant reduction in CO2 uptake with the existence of trace amounts of water vapor. The effect of water, however, is found to be quantitatively different between Mg- and Zn-MOF-74.