摘要
采用密度泛函B3LYP方法对Zn(Ⅱ)在水锰矿(MnOOH)2(H2O)6簇模型表面的水合、一级和二级水解三类共11种吸附构型进行了理论研究.计算结果表明,水合吸附构型的稳定性顺序为DC(双角)>SE-B(单边-B)>SE-A(单边-A)>DE(双边),水解吸附构型的稳定性顺序为DC>SE-A>SE-B>DE,均符合鲍林第三规则;热化学分析结果说明,其吸附和水解是相互制约的两个过程,这一结论通过前线轨道理论分析得到了证明;自然布居分析结果表明,吸附过程中电子由簇模型向吸附质迁移;结合电子供体-受体相互作用和前线轨道组成分析了吸附产物的稳定性.
Three kinds of adsorption species （hydrated, 1st hydrolysis and 2nd hydrolysis ） in Zn Zn（Ⅱ）/γ-MnOOH system were calculated with DFT-B3LYP method. The thermochenfistry analysis indicate that the stability order of the adsorption species was DC 〉 SE-B 〉 SE-A 〉 DE for the hydrated species, and DC 〉 SE-A 〉 SE-B 〉 DE for hydrolysis species, which obeyed the 3rd law of Pauling. The adsorptive process and hydrolytic process always show an inter-antagonistic relationship in this system, which is also consistent with the frontier molecular orbital analysis. Natural population analysis indicate that electronic transfer from cluster model to Zn-O unit was occurred clearly during adsorptive process, which give a reasonable explanation for the stabilization of adsorption species combining with electronic donor-acceptor and frontier molecular orbital analysis.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2008年第9期1804-1809,共6页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:20677053)
新世纪优秀人才支持计划(批准号:NCET-07-0783)资助
关键词
密度泛函理论
Zn(Ⅱ)
水锰矿
吸附构型
Density functional theory
Zn（Ⅱ）
γ-MnOOH
Adsorption configuration
