Vibrational frequencies of CO on Pt(111) in electric field: A periodic DFT study

被引:25
作者
Lozovoi, A. Y. [1 ]
Alavi, A.
机构
[1] Queens Univ Belfast, Sch Math & Phys, Atomist Simulat Ctr, Belfast BT7 1NN, Antrim, North Ireland
[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
基金
英国工程与自然科学研究理事会;
关键词
vibration; stark shift; carbon monoxide; platinum; ab initio;
D O I
10.1016/j.jelechem.2007.02.030
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
The stretching frequency of CO adsorbed on Pt(1 1 1), vc-0, changes if an external electric field F is applied (the vibrational Stark effect). The slope dv(c-o)/dF measured in electrochemical cells, is a factor of two larger than that obtained in UHV experiments. The reasons for this discrepancy are still being debated, whereas existing DFT calculations "support" the electrochemical value. This study, on the contrary, produces a slope close to that found in UHV. The difference between our ab initio calculations and previous studies is that the latter were performed with finite clusters, whereas here the electric field is applied to a periodic supercell. This highlights the importance of the computational setup, and in particular the boundary conditions, for calculations of charged systems. (c) 2007 Elsevier B.V. All rights reserved.
引用
收藏
页码:140 / 146
页数:7
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