Density functional study of CO on Rh(111) -: art. no. 165405

被引：345

作者：

Köhler, L

Kresse, G

机构：

[1] Univ Vienna, Inst Mat Phys, A-1090 Vienna, Austria

[2] Univ Vienna, Ctr Computat Mat Sci, A-1090 Vienna, Austria

来源：

PHYSICAL REVIEW B | 2004年 / 70卷 / 16期

关键词：

D O I：

10.1103/PhysRevB.70.165405

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

We present detailed density functional calculations for CO on Rh(111). At low coverage, the applied semilocal functionals clearly favor CO adsorption in the hollow site. This is in disagreement with experimental studies which all point towards atop adsorption at low coverage. The experimental assignment is confirmed by theoretical calculations of the vibrational frequencies and core level shifts at various coverages, ranging from 1/9 to 3/4 [(2x2)-3CO] monolayer CO. For atop adsorption the calculated vibrational frequencies and the Rh surface core level shifts are indeed found to agree very well with experiment. To understand these controversial results, a molecular GGA+U method is applied, which allows one to shift the CO 2pi* orbital towards the vacuum level. This reduces the binding energy in the hollow site and brings the theoretical site preference in agreement with experiment. It is investigated how this molecular GGA+U method influences the vibrational properties and the surface core level shifts. Furthermore, details on the molecular GGA+U method are presented.

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页码：1 / 9

页数：9

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