催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (8): 696-702.

• 研究论文 • 上一篇    下一篇

氧在CuCl(111)表面吸附的密度泛函理论研究

王霞1,陈文凯1,徐香兰1,陆春海2   

  1. 1 福州大学化学系, 福建福州 350002; 2 成都理工大学核技术与自动化工程学院, 四川成都 610059
  • 收稿日期:2007-08-25 出版日期:2007-08-25 发布日期:2011-08-19

A Density Functional Theoretical Study on the Chemical Adsorption of Oxygen on CuCl(111) Surface

WANG Xia1, CHEN Wenkai1*, XU Xianglan1, LU Chunhai2   

  1. 1 Department of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China; 2 College of Applied Nuclear Technology and Automation Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
  • Received:2007-08-25 Online:2007-08-25 Published:2011-08-19

PDF

1188

被引次数

9

摘要： 运用广义梯度密度泛函理论的PW91方法结合周期平板模型,在DNP基组下研究了氧分子和氧原子在CuCl(111)表面上的吸附. 对氧分子在CuCl(111)表面吸附的相关计算和比较发现,覆盖度为0.25单层时的吸附构型为稳定的吸附构型,氧分子倾斜地吸附在CuCl(111)表面的顶位时比较稳定,吸附后O2分子的伸缩振动频率与自由O2分子相比发生了红移. 态密度和Mulliken电荷布居分析结果表明,整个吸附体系发生了由Cu原子向O2分子的电荷转移. 氧原子在CuCl(111)表面吸附的计算结果表明,氧原子倾向于以穴位(hollow)吸附在CuCl(111)表面,通过Mulliken电荷布居和态密度分析对氧原子在CuCl表面的吸附行为作了进一步探讨.

关键词: 密度泛函理论, 吸附, 氧气, 氯化亚铜, 周期平板模型

Abstract: The adsorption of O2 molecules and O atoms on the CuCl(111) surface was studied using first-principle calculations based on the density functional theory with the generalized gradient approximation developed by Perdew and Wang (PW91). Adsorption models under different coverages of the CuCl(111) surface were considered. The adsorption over various adsorption sites (top-V, hollow-V, bridge-V, Cl-V, top-P, hollow-P, bridge-P, and Cl-P sites) was selected for calculation. The optimized results indicated that the adsorption was very stable when the coverage was set to 0.25 monolayer. The O2 molecule was inclined to adsorb aslant on the CuCl(111) surface, and theO-Ostretching vibrational frequencies were significantly red-shifted. The results of the Mulliken population analysis and the density of states indicated that the charges transferred from Cu to oxygen. The O atom was likely to adsorb at the hollow site of the CuCl(111) surface. The Mulliken population analysis and the density of states were calculated to explain the computed results.

Key words: density functional theory, adsorption, oxygen, cuprous chloride, periodical slab model