期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 117, 期 28, 页码 14502-14509出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp402594x
关键词
-
资金
- Ministerio de Economia y Competitividad (Spain) [MAT2012-31526, CSD2008-0023]
- European FEDER
The outstanding catalytic properties of cerium oxides and, consequently, the broad use in heterogeneous catalysis rely on the easy Ce3+ <-> Ce4+ redox conversion. Within the two-state model of Marcus, the electron transfer associated with the redox process is governed by the electronic coupling matrix element V-AB that accounts for the interaction between the diabatic electronic states at the crossing seam. Here we present a computational analysis based on ab initio quantum mechanics theory that allows for a characterization of negative polaron structures and intrinsic polaron hopping in bulk CeO2. The relevant parameters inherent to the model: reorganization energy, activation barrier, and electronic coupling for the 4f -> 4f electron hopping are estimated for several models. Our analysis predicts an activation barrier of 0.4 eV and a transmission coefficient kappa = 0.81, confirming the earlier proposed adiabatic theory of small polaron and hopping conductivity in reduced bulk ceria.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据