Zn(H_2O)_n^(2+)(n=1～10)水合团簇的结构与光谱性质  

Structure and spectral properties of Zn(H_2O)_n^(2+)(n=1-10) hydrate clusters

作　　者：丁治英[1] 敬珊珊[1] 

机构地区：[1]中南大学化学化工学院,长沙410083

出　　处：《中国科技论文》2015年第24期2863-2867,共5页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金资助项目(20120162120028);国家自然科学基金资助项目(51404299)

摘　　要：为了研究锌氨浸过程中氨分子取代水分子的机理,采用量子化学计算方法 B3LYP/6—311++g(2df,2p),对气相和水相中Zn(H_2O)_n^(2+)(n=1~10)水合团簇的几何结构进行了研究。根据水合能可知:在气相中,当水分子数n=6~10时,Zn(H_2O)_n^(2+)水合团簇的六配位结构较稳定,而在水相中,其五配位和六配位均有稳定构型;当n=10时,还不足以形成Zn^(2+)的近似饱和水合层。Zn(H_2O)_n^(2+)水合团簇的Zn—O键长和Zn^(2+)的电荷密度均随水分子数的增加而减小。五配位结构的红外光谱和拉曼光谱与文献报道的实验值很接近,表明五配位结构的Zn(H_2O)_n^(2+)(n=5~10)水合团簇很可能是锌湿法冶金溶液的Zn^(2+)(aq)物种。To investigate the mechanism of water molecule substituted by ammonia molecule in zinc ammonia leaching process,the structures of Zn（H2O）n^2＋（n=1-10）clusters in gas and aqueous phases have been studied using the B3LYP/6-311＋＋g（2df,2p）method.According to the hydration energy,Zn（H2O）n^2＋clusters favor six coordinated structures for n = 6-10 in gas phase,while five or six coordinated conformers are favored in aqueous phase.The approximate saturated hydration water is not formed even if nis 10.The Zn-O bond length of Zn（H2O）n^2＋clusters and charge population of Zn^2＋ decrease with the increase of water molecules.The infrared and raman spectrum of five coordinated structures are consistent with the experimental values in literatures,which indicates that five coordinated conformer of Zn（H2O）n^2＋（n=5-10）clusters is Zn（aq）^2＋species in zinc solution of hydrometallurgy.

关 键 词：配位化学 水合锌离子 水合团簇 量化计算 稳定结构 

分 类 号：O641.1[理学—物理化学]