单个金属原子掺杂贵金属小团簇结构与物性的理论研究

项目名称： 单个金属原子掺杂贵金属小团簇结构与物性的理论研究

项目编号： No.11464008

项目类型： 地区科学基金项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 胡朝浩

作者单位： 桂林电子科技大学

项目金额： 50万元

中文摘要： 双金属小团簇因存在显著的量子尺寸效应、表面效应、元素协作效应等作用而呈现出独特的物理化学性质，已受到国内外学者的高度关注，但当前的实验手段仍不能足够胜任其结构和尺寸大小的精确表征。本课题拟将采用进化模拟结构预测技术，结合第一性原理计算，理论预测贵金属小团簇Xn（X = Au，Ag，Cu，Pd，Pt；n = 3-20）掺杂单个金属原子Me（Me = Fe，Co，Ni，Ce，Gd，Pr，X）的双金属团簇Me@Xn结构，进行结构几何优化、结合能、能量二阶差分、HOMO-LUMO能隙、磁矩等电子结构计算，调查团簇结构与物性参数随尺寸和掺杂元素变化的演化规律，同时对具有独特结构和较高稳定性的团簇进行H2、CO、O2等小分子吸附行为的计算研究，探讨团簇对气体小分子的氧化或还原反应的作用机理，理论设计出具有新奇光学、磁学或催化性质的新型Me@Xn团簇，为后续的的实验研究提供重要的理论依据和基础物性数据。

中文关键词： 金属团簇；进化模拟；第一性原理计算；贵金属；结构与性质

英文摘要： Small bimetallic clusters exhibit many peculiar physical and chemical properties and have attracted much attention due to the prominent quantum size effect, surface effect, and synergistic effect between different elements.The current experimental techniques, however, are still not sufficient for the accurate characterization on the structure and dimension size of small clusters. Using the evolutionary simulation technique for structure prediction and combining with first-principles calculations this research aims to predict the structure of bimetallic clusters Me@Xn in which the small noble metal clusters Xn (X = Au, Ag, Cu, Pd, Pt, n = 3 -20) are doped by a single metal atom Me (Me = Fe, Co, Ni, Ce, Gd, Pr, X). The geometry optimizations, binding energies, sencond differences in energy, HOMO-LUMO gaps, and magnetic moments of Me@Xn clusters are calculated in order to investigate the evolution of structures and physical properties changing with the dimension size and doping elements. To elucidate the oxidation or reduction mechanism of bimetallic clusters to small molecules, the absorption behaviors of some small molecules such as H2, CO, and O2 on some Me@Xn clusters with specific structure and higher stability are further investigated. The ultima goal of this research is to design theoretically the new Me@Xn clusters with novel optical, magnetic or catalytic properties in order to provide the important theoretical grounds and fundamental physical data for the subsequent experiments.

英文关键词： Metal cluster;Evolutionary simulation;First-principles calculation;Noble metal;Structure and property