Polarizable Site Charge Model at Liquid/Solid Interfaces for Describing Surface Polarity: Application to Structure and Molecular Dynamics of Water/Rutile TiO2(110) Interface

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• 作者：Hisao Nakamura ; Tatsuhiko Ohto ; Yuki Nagata
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：February 12, 2013
• 年：2013
• 卷：9
• 期：2
• 页码：1193-1201
• 全文大小：441K
• 年卷期：v.9,no.2(February 12, 2013)
• ISSN：1549-9626

文摘

We present a novel scheme to construct a polarizable force field for liquid/solid interfaces, which takes into account the effect of the surface polarity induced by liquid鈥搒olid interactions explicitly. We extend the charge response kernel (CRK) method for molecules to solid surfaces by introducing the surface CRK. The CRK parameters are systematically determined by the first-principles calculations in the slab model with the dipole-correction method. Our methodology is applied to the water/clean rutile TiO₂(110) interface. Structures and induced charges of a single water molecule attached to the TiO₂ surface optimized by our polarizable force field show good agreement with those predicted by the first-principles calculations. Further, we carried out MD simulations for the liquid water/TiO₂ interface and found three stable structures of water attached to the TiO₂ surface. Two of them are predicted by both the polarizable and the nonpolarizable force fields, while the polarizable force field model predicts a structure of water with the hydrogen and oxygen atoms interacting with the oxygen atom of the surface TiO₂ and the hydrogen atom of the other water molecule, respectively, which was reported by the previous first-principles MD simulation. This indicates that the dipole moments of water and TiO₂ induced by the water鈥揟iO₂ interactions have significant impact on molecular conformations of the water/TiO₂ interface.