Analysis of electronic contributions to the vibrational frequency of CO/Cu2O(111)

被引:30
作者
Bredow, T
Márquez, AM
Pacchioni, G
机构
[1] Univ Milan, Dipartimento Sci Mat, Ist Nazl Fis Mat, I-20125 Milan, Italy
[2] Univ Seville, Dept Quim Fis, E-41012 Seville, Spain
关键词
ab initio quantum chemical methods and calculations; carbon monoxide; chemisorption; copper (I) oxide Cu2O; density functional calculations; single-crystal surface; vibrations of adsorbed molecules;
D O I
10.1016/S0039-6028(99)00427-6
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
The change in the CO vibrational frequency after adsorption on low-coordinated copper atoms at the Cu2O(111) surface has been studied theoretically with gradient-corrected density-functional theory (DFT) methods. The surface was modeled with a Cu28O14 cluster embedded in point charges and total-ion model potentials. An analysis of the contributions to changes in the CO stretching mode based on the electron density was performed. We show that the proper description of the Cu 3d-->CO 2 pi* back donation, which is responsible for the experimentally observed small red shift, requires the inclusion of electron correlation in a self-consistent way. In addition to this main physical effect, the absolute value of the frequency shift depends on the form of the exchange functional and on the description of electrostatic interactions in the cluster model. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:137 / 145
页数:9
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