密度泛函方法研究卤族原子(FBrI)-上海有机化学研究所.PDF

2007 年第65 卷 化 学 学 报 Vol. 65, 2007 第14 期, 1294～1298 ACTA CHIMICA SINICA No. 14, 1294～1298 ·研究论文· 密度泛函方法研究卤族原子(F, Br, I)与银原子簇的相互作用 赵 爽 李振华 刘智攀 王文宁 范康年* (复旦大学化学系 上海市分子催化和功能材料重点实验室 化学物理研究中心 上海 200433) 摘要 应用密度泛函理论计算方法研究了气相中的单个的F, Br, I 原子吸附在中性和带正、负电荷的银原子团簇上的平 衡几何构型 AgnX0,±1 (X ＝F, Br, I) 、吸附能、电荷转移量以及碎片化模式, 并与先前研究过的氯原子在银原子簇上的吸 附做了对比. 结果表明卤族原子在银原子簇上的吸附得到的相似的最稳定几何构型, 具有相似的吸附性质. 吸附能和 电子转移量的大小顺序为F ＞Cl ＞Br ＞I, 与电负性顺序相一致. 关键词 密度泛函方法; 银原子簇; 卤族原子 Density Functional Study of the Interaction of Halogen Atom (F, Br, I) with Silver Clusters ZHAO, Shuang LI, Zhen-Hua LIU, Zhi-Pan WANG, Wen-Ning FAN, Kang-Nian* (Center for Chemical Physics, Key Laboratory of Molecular Catalysis and Inovative Materials, Department of Chemistry, Fudan University, Shanghai 200433) Abstract The binding of fluorine, bromine or iodine atom to small neutral, anionic or cationic silver clus- 0, 1 ters Agn ± (n ＝2～7) has been studied by using the PW91PW91 density functional method. The binding energy, binding pattern, electronic structure and dissociation channel have been explored, in comparison with the previous study of chlorine binding to silver clusters. Calculations show that the most stable struc- tures of complexes, Ag X0,±1 (X ＝F, Br and I) and Ag Cl0,±1, often have similar structures and binding pat- n n terns. The binding energy and electron transfer ability are