Thickness-Dependent Hydroxylation of MgO(001) Thin Films

被引：58

作者：

Carrasco, Esther ^{[1
]}

Brown, Matthew A. ^{[1
]}

Sterrer, Martin ^{[1
]}

Freund, Hans-Joachim ^{[1
]}

Kwapien, Karolina ^{[2
]}

Sierka, Marek ^{[2
]}

Sauer, Joachim ^{[2
]}

机构：

[1] Fritz Haber Inst Max Planck Gesellschaft, Dept Chem Phys, D-14195 Berlin, Germany

[2] Humboldt Univ, Dept Chem, D-10099 Berlin, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2010年 / 114卷 / 42期

关键词：

DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; AUGMENTED-WAVE METHOD; WATER DISSOCIATION; AB-INITIO; ELECTRONIC-STRUCTURE; AMBIENT CONDITIONS; MGO(100) SURFACES; AQUEOUS-SOLUTIONS; MGO SURFACE;

D O I：

10.1021/jp105294e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Hydroxylation of MgO surfaces has been studied from UHV to mbar pressure for MgO(001) films of different thickness grown on Ag(001) by X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, and density functional theory calculations. In agreement with earlier studies on MgO(001) single crystals, a threshold water pressure on the order of 10(-4) mbar is found for extensive hydroxylation of thick, bulklike MgO films. Decreasing the MgO film thickness shifts the threshold pressure to lower values, being 10(-6) mbar in the limit of 2 monolayer MgO(001)/Ag(001). This result is explained on the basis of the precursor state of periclase MgO(001) dissolution involving hydrolysis of Mg-O surface bonds. The enhanced structural flexibility (polaronic distortion) of the ultrathin MgO film facilitates surface hydroxylation by lowering the barrier for hydrolysis.

引用

页码：18207 / 18214

页数：8

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