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20K下铑(111)表面的水吸附:从单体到块状非晶冰

Water adsorption on Rh(111) at 20 K: from monomer to bulk amorphous ice.

作者信息

Yamamoto Susumu, Beniya Atsushi, Mukai Kozo, Yamashita Yoshiyuki, Yoshinobu Jun

机构信息

The Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan.

出版信息

J Phys Chem B. 2005 Mar 31;109(12):5816-23. doi: 10.1021/jp044379d.

Abstract

The adsorption of water (D(2)O) molecules on Rh(111) at 20 K was investigated using infrared reflection absorption spectroscopy (IRAS). At the initial stage of adsorption, water molecules exist as monomers on Rh(111). With increasing water coverage, monomers aggregate into dimers, larger clusters (n = 3-6), and two-dimensional (2D) islands. Further exposure of water molecules leads to the formation of three-dimensional (3D) water islands and finally to a bulk amorphous ice layer. Upon heating, the monomer and dimer species thermally migrate on the surface and aggregate to form larger clusters and 2D islands. Based on the temperature dependence of OD stretching peaks, we succeeded in distinguishing water molecules inside 2D islands from those at the edge of 2D islands. From the comparison with the previous vibrational spectra of water clusters on other metal surfaces, we conclude that the number of water molecules at the edge of 2D islands is comparable with that of water molecules inside 2D islands on the Rh(111) surface at 20 K. This indicates that the surface migration of water molecules on Rh(111) is hindered as compared with the cases on Pt(111) and Ni(111) and thus the size of 2D islands on Rh(111) is relatively small.

摘要

利用红外反射吸收光谱(IRAS)研究了20K下重水(D₂O)分子在Rh(111)上的吸附情况。在吸附初始阶段,水分子以单体形式存在于Rh(111)上。随着水覆盖度的增加,单体聚集成二聚体、更大的团簇(n = 3 - 6)以及二维(2D)岛状结构。进一步暴露水分子会导致三维(3D)水岛的形成,最终形成块状非晶冰层。加热时,单体和二聚体物种在表面热迁移并聚集形成更大的团簇和2D岛状结构。基于OD伸缩峰的温度依赖性,我们成功区分了2D岛内的水分子和2D岛边缘的水分子。通过与其他金属表面水团簇的先前振动光谱进行比较,我们得出结论,在20K时,Rh(111)表面2D岛边缘的水分子数量与2D岛内的水分子数量相当。这表明与Pt(111)和Ni(111)表面的情况相比,Rh(111)上水分子的表面迁移受到阻碍,因此Rh(111)上2D岛的尺寸相对较小。

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