蒙脱石晶体结构构型及其XRD、IR的分子模拟Molecular Simulations of Crystal Structure Conformation,X-Ray Diffraction and Infra-Red Spectrum in Montmorillonites
王进;王军霞;曾凡桂;吴秀玲;
摘要(Abstract)：
利用Cerius2软件分别构建了15种含有0～96个水分子的Li-、Na-、K-蒙脱石超晶格模型。分析了模型结构中的键长和键角,运用分子力场方法—UFF力场构型优化得到蒙脱石的最优构型及其总能量等参数,在此基础上计算了3种蒙脱石含有32、64和96个水分子时晶体结构的X射线衍射(XRD)和红外吸收光谱(IR)。结果表明,蒙脱石结构模型中键长和键角等参数说明其结构具有合理性;当蒙脱石的结构达到能量最小构型时,体系的总能量随着水含量的增加而降低;XRD的模拟结果和实验结果相一致;IR的模拟结果与实验结果有所偏离,可能是由选取的分子力场和分子位能模型所致。
关键词(KeyWords)： 蒙脱石;结构构型;XRD;IR;分子模拟
基金项目(Foundation): 国家自然科学基金项目(批准号:4000200940372073);; 西南科技大学“核废物与环境安全”国防重点学科实验室培育基金项目(08zxnp03)
作者(Authors): 王进;王军霞;曾凡桂;吴秀玲;
DOI: 10.16461/j.cnki.1000-4734.2011.01.020
参考文献(References)：
- [1]杨雅秀,张乃娴,苏昭冰,等.中国粘土矿物[M].北京:地质出版社,1994:104-133.
- [2]潘兆橹,万朴.应用矿物学[M].武汉:武汉工业大学出版社,1993:216-221.
- [3]Boek E S,Coveney P V,Skipper N T.Monte Carlo molecular modeling studies of hydrated Li-,Na-,and K-smectites:understanding therole of potassium as a clay swelling inhibitor[J].J Am Chem Soc,1995,117:12608-12617.
- [4]Young D A,Smith D E.Simulation of clay mineral swelling and hydration:Dependence upon interlayer ion size and charge[J].J PhyChem B,2000,104:9163-9170.
- [5]Marry V,Turq P,Cartailler T,et al.Microscopic simulation of structure and dynamics of water and counterions in a monohydrated montmo-rillonite[J].J Chem Phys,2002,117:3454-3463.
- [6]Chang F-R C,Skipper N T,Sposito G.Monte Carlo and molecular dynamics simulations of interfacial structure in lithium-montmorillonitehydrates[J].Langmuir,1997,13:2074-2082.
- [7]Odriozola G,Aguilar J F.Stability of K-montmorillonite Hydrates:Hybrid MC simulations[J].J Chem Theory Comput,2005,1(6):1211-1220.
- [8]Kosakowski G,Churakov S V,Thoenen T.Diffusion of Na and Cs in montmorillonite[J].Clays Clay Miner,2008,56(2):190-206.
- [9]王进,曾凡桂,王军霞.钠蒙脱石水化膨胀和层间结构的分子动力学模拟[J].硅酸盐学报,2005,33(8):996-1001.
- [10]王进,曾凡桂,王军霞.蒙脱石膨胀特性的分子力学模拟[J].地球化学,2007,36(1):103-108.
- [11]王进,王军霞,曾凡桂.钾基蒙脱石的分子力学和分子动力学模拟[J].硅酸盐学报,2009,37(4):554-560.
- [12]Hisako S,Akihiko Y,Katsuyuki K.Molecular simulation for flexibility of a single clay layer[J].J Phys Chem B,2001,105:7990-7997.
- [13]Pospiysil M,CapkováP,Weiss Z,et al.Structrue analysis of montmorillonite intercalated with cetylpyridinium and cetyltrimethylammoni-um:molecular simulations and XRD analysis[J].J Colloid Interface Sci,2002,245:126-132.
- [14]Liu X D,Lu X C,Wang R C,et al.Interlayer structure and dynamics of alkylammonium-intercalated smectites with and without water:Amolecular dynamics study[J].Clays Clay Miner,2007,55(6):554-564.
- [15]Boek E S,Sprik M.Ab initio molecular dynamics study of the hydration of a sodium smectite clay[J].J Phys Chem B,2003,107:3251-3256.
- [16]Stackhouse S,Coveney P V.Study of thermally treated lithium-montmorillonite by ab initio methods[J].J Phys Chem B,2002,106:12470-12477.
- [17]Frenkel D,Smit B.分子模拟–从算法到应用[M].汪文川,周健,曹大鹏,等(译).北京:化学工业出版社,2002:329-338.
- [18]Hi L S,Rasaiah J C.Molecular dynamics simulation of ion mobility.2.Alkali metal and halide ions using the SPC/E model for water at25℃[J].J Phys Chem,1996,100:1420-1425.
- [19]Refson K,Park S H,Sposito G.Ab initio computational crystallography of 2∶1 clay minerals:1.Pyrophyllite-1 Tc[J].J Phys Chem B,2003,107:13376-13383.