二聚物X_(2)和XK(X=Mn,Fe,Co,Ni,Cu)吸附NO的密度泛函理论研究

Density functional theory study the adsorption of NO by dimers X_(2)and XK(X=Mn,Fe,Co,Ni,Cu)

为有效降低NO对环境以及人体造成的危害,着重从催化剂入手,研究过渡金属Mn_(2),Fe_(2),Co_(2),Ni_(2),Cu_(2)及K掺杂的MnK,FeK,CoK,NiK,CuK的二聚物对NO的吸附性能.采用密度泛函理论的B3LYP,B3PW91,B3P86,B1B95以及PBE1PBE方法结合LANL2DZ,SDD,CEP-121G基组,采用B3LYP,B3PW91,B3P86以及PBE1PBE方法结合6-31++G(3df,3pd),6-311++G(3df,3pd),6-31G(d,p),LANL2DZ,SDD基组分别系统研究了X_(2)和XK(X=Mn,Fe,Co,Ni,Cu)团簇和NO的几何结构,计算出其键长,频率,离解能,再与对应的实验值进行对比.进一步采用PBE1PBE方法结合LANL2DZ和6-31G(d,p)基组研究了X_(2)NO和KXNO团簇的几何结构,计算出各原子间键长和吸附能.结果表明,XKNO团簇的吸附能是最小的,KXNO团簇的吸附能次之,X_(2)NO团簇的吸附能最大.即K吸附NO时能发生更好的反应.

In order to reduce the harm of NO to the environment and human effectively,we focus on the catalysis and study the ability to adsorb NO of transition metals Mn_(2),Fe_(2),Co_(2),Ni_(2),Cu_(2)and K-doped MnK,FeK,CoK,NiK,CuK dimers.We investigate the geometric structures of NO and X_(2)and XK(X=Mn,Fe,Co,Ni,Cu)clusters systematically by using density functional theory B3LYP,B3PW91,B3P86,PBE1PBE under 6-31++G(3df,3pd),6-311++G(3df,3pd),6-31G(d,p),LANL2DZ,SDD basis sets and B3LYP,B3PW91,B3P86,B1B95,PBE1PBE under LANL2DZ,SDD,CEP-121G basis sets,respectively.And the bond lengths,frequencies,dissociation energies are calculated at the same level,then compared with the corresponding experimental values.Further using the PBE1PBE method combined with the LANL2DZ and 6-31G(d,p)basis sets to study the geometric structures of the X_(2)NO and KXNO clusters,and calculate the bond lengths and adsorption energies between each atom.The results show that the adsorption energy of XKNO clusters is the smallest,followed by the adsorption energy of KXNO clusters,and the adsorption energy of X_(2)NO clusters is the largest.That is,a better reaction occurs when K adsorbs NO.