CAJ | 학술논문

用高斯程序的B3LYP交换相关函数和全电子基组DGDZVP、TZVP优化Nin、Nin+和Nin-(n =2 ～8),得到这些体系的基态几何构型、离化能、电子亲和能及键能.结果表明:Ni2,Ni3,Ni4,Ni5和Ni6团簇的基态分别是5,7,9,11和13重态.表明:Ni2,Ni3,Ni4,Ni5和Ni6团簇中分别有4,6,8,10和12个平行自旋的电子,在每一个Nin团簇中非耦合的电子最多,这些电子占据不同的轨道,导致每一个Nin团簇的能量最小,说明在这些Nin团簇中电子平行的效应大于电子耦合的效应,这显然与d电子的离域效应有关,称为自旋极化效应,符合宏特规则.Nin、Nin+和Nin-(n =2 ～8)体系的磁矩分别是Nin具有8μB(n=6～8),Nin+具有9μB(n=6～8),Nin-具有7μB(n=4～8).
용고사정서적B3LYP교환상관함수화전전자기조DGDZVP、TZVP우화Nin、Nin+화Nin-(n =2 ～8),득도저사체계적기태궤하구형、리화능、전자친화능급건능.결과표명:Ni2,Ni3,Ni4,Ni5화Ni6단족적기태분별시5,7,9,11화13중태.표명:Ni2,Ni3,Ni4,Ni5화Ni6단족중분별유4,6,8,10화12개평행자선적전자,재매일개Nin단족중비우합적전자최다,저사전자점거불동적궤도,도치매일개Nin단족적능량최소,설명재저사Nin단족중전자평행적효응대우전자우합적효응,저현연여d전자적리역효응유관,칭위자선겁화효응,부합굉특규칙.Nin、Nin+화Nin-(n =2 ～8)체계적자구분별시Nin구유8μB(n=6～8),Nin+구유9μB(n=6～8),Nin-구유7μB(n=4～8).
Density functional theory B3LYP are performed in study on structure of Nin,Nin+ and Nin-(n =2-8).DGDZVP all-electron basis sets and TZVP all-electron basis sets are employed. Equilibrium geometries, ionization potentials,electron affinities and binding energies are obtained.It shows that the ground state of Ni2,Ni3,Ni4,Ni5 and Ni6 cluster are 5-,7-,9-,11-,and 13-multiple state,respectively,which indicates spin polarization effect in Nin (n ≤ 8 )clusters is important.That is,there are 4,6,8,10,and 12 parallel spin electrons iu Ni2,Ni3,Ni4,Ni5 and Ni6 cluster,respectively.Number of non-conjugated electrons in ground state cluster is the greatest.These electrons occupy different spacious orbitals so that energy of Nin (n≤8) cluster is minimized.It can be concluded that effect of parallel spin in Nin (n ≤8) clusters is greater than effects of conjugated clusters,which is obviously related to electron d delocalization.This is spin polarization effect of Nin (n ≤ 8) clusters,which is a result of the Hund' s rule.Moreover,we find that spin magnetic moments of Nin(n=6-8) are 8 μB,those of Nin +(n=6-8) are 9 μB and those of Nin-(n=4-10) are7 μB.