Adsorption of water on NaNO3(001) surface from first-principles calculations.
Adsorption of water on NaNO3(001) surface from first-principles calculations.
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DOI：
10.1016/j.jcis.2012.11.004
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发表时间：
2013-03
影响因子：
9.9
通讯作者：
Jinyong Luo;Ai Hu;Xiao-lin Wang;Yun-hong Zhang;Zesheng Li
中科院分区：
文献类型：
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作者：
Jinyong Luo;Ai Hu;Xiao-lin Wang;Yun-hong Zhang;Zesheng Li
采用密度泛函理论（DFT）方法研究了水单体、水分子团簇在NaNO 3（001）表面的吸附行为。单个水分子更容易位于桥位，其H原子被硝酸根离子的O原子吸引，其O原子邻近Na+。Mulliken布居分析表明，较少的电子从基板的Na原子转移到水分子。系统地研究了水分子团簇在NaNO 3（001）表面上的吸附行为，结果表明，当水分子团簇在NaNO 3（001）表面上的吸附量为1 ML时，四个水分子之间通过氢键形成水链。有趣的是，水分子通过氢键连接形成14元大环水环，在NaNO 3（001）表面上吸附1.5ML。我们估计的O-H对称伸缩频率（νO-H）随水覆盖度的减小而发生蓝移，这与实验给出的趋势一致。
Density functional theory (DFT) calculations were applied to investigate the adsorption of water monomer, water clusters on NaNO3(001) surface. Single water molecule is more likely to locate on the bridge site with its H atom attracted by the O atom of nitrate ion and its O atom adjacent to Na+. Mulliken population analysis shows that fewer electrons transfer from the Na atom of substrate to water molecule. A systematic study of water clusters adsorption at high coverages ranging from 0.5 monolayer (ML), 0.75ML, 1ML, 1.25ML, and 1.5ML on NaNO3(001) surface was also investigated, and the results indicate that for 1ML water adsorption on NaNO3(001) surface, a water chain is formed among four water molecules through hydrogen bonds. Interestingly, the water molecules are linked through hydrogen bonds to form a 14-membered macrocyclic water ring for 1.5ML adsorption on NaNO3(001) surface. Our estimated O–H symmetric stretching frequency (νO–H) will have blueshift with decrease of water coverage, which is consistent with the tendency given by experiments.