AMT在青铜器文物表面形成缓蚀膜的计算分析  

Calculated analysis on the inhibition interaction formed film of bronze cultural relics surface by AMT

作　　者：姜丽艳[1] 庞丽纹[1] 李晓东[2] 安梅梅[3] 

机构地区：[1]内蒙古化工职业学院化学工程系,呼和浩特010010 [2]天水师范学院生命科学与化学化工学院,天水741001 [3]天水师范学院文史学院,天水741001

出　　处：《原子与分子物理学报》2015年第1期26-34,共9页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金项目(51063006);国家社会科学基金项目(13CMZ011)

摘　　要：利用密度泛函(DFT)、概念DFT、Electron Localization Function(ELF)和Fukui函数中的亲电反应函数及Multiwfn软件,在B3LYP/6-311+G(d,p)基组水平上研究了5-氨基-2-巯基-1,3,4-噻二唑[AMT(a)]及其同分异构体[AMT(b)]和四面体型配合物i Thiol-Cu-2AMT的几何构型和反应特性.通过计算研究发现,首先AMT(b)与青铜器表面的Cu2+形成平面型配合物i Thiol-Cu后再与AMT(b)相互作用,并最终形成不规则的四面体型i Thiol-Cu-2AMT.在i Thiol-Cu-2AMT中Cu19能与AMT(b)中的亲核性原子有效地结合,形成四面体结构后将Cu19离子保护起来,达到了保护青铜器不受腐蚀的目的;对i Thiol-Cu-2AMT结构中的活性位置分析及ELF拓扑研究后发现,在i Thiol-Cu-2AMT中N6、N15、S26和S35原子又可以与其它的Cu2+相互作用,逐步形成配位型聚合物保护膜[i Thiol-Cu-2AMT]n.The 2 -aminino- 5 -mercapto- 1,3,4 -thiadizole （AMT （a）） and the corresponding isomer AMT （b） Were studied by using the density functional theory （DFT）, election localization function （ELF）, electrophilie reaction functional of Fukui wavefunction analyzer and Multiwfn software methods. The geometries of coordinate protective films unit （ iThiol - Cu - 2AMT） were also optimized by B3 LYP/6 - 311 ＋ G （ d, p） and the above methods. The calculated results indicate that the planar framework complex iThiol - Cu is formed firstly via AMT （b） and Cu2＋ of the exterior bronze, and then the irregular tetrahedral framework complex iThiol -Cu - 2AMT is formed on iThiol - Cu and Cu^2＋. It is found that the Cul9 atom of iThiol - Cu - 2AMT unit is enwrapped in the tetrahedral framework, and its reaction activity is reduced. In addition, the active reaction location of ithiol - Cu - 2AMT were analyzed by Muhiwfn analyzer and ELF topology methods, the results show that the new coordinated bond N - Cu and covalent bond S - Cu are formed by the interactions of N6, N15, $26 and S35 atoms with other Cu^2＋ cations. The theoretical study results explain the formation of the high polymer film [ iThiol- Cu-2AMT] n in the case of situation.

关 键 词：青铜器文物保护 四面体型配合物i Thiol-Cu-2AMT 理论研究 密度泛函 

分 类 号：O641[理学—物理化学]