CALCULATION BY ANALYTICAL AND LOCAL-DENSITY HARTREE-FOCK METHODS OF SPIN AND CHARGE-DENSITIES IN THE V(II) HEXAAQUA ION

被引:4
|
作者
CHANDLER, GS [1 ]
CHRISTOS, GA [1 ]
FIGGIS, BN [1 ]
GRIBBLE, DP [1 ]
REYNOLDS, PA [1 ]
机构
[1] UNIV WESTERN AUSTRALIA,DEPT CHEM,NEDLANDS,WA 6009,AUSTRALIA
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1992年 / 88卷 / 14期
关键词
D O I
10.1039/ft9928801953
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Calculations on a V(OH2)62+ ion in the experimental geometry have been performed with conventional ab initio and with discrete-variational local-density functional approximation unrestricted Hartree-Fock methods. In each case a variety of basis sets was employed. The charge and spin distributions produced were compared with each other, and the latter with experimental results from a polarized neutron diffraction experiment on (ND4)2V(SO4)2 6D2O. If the DZP ab initio results are taken as the benchmark, the charge-difference and the spin-density maps of the LDF methods are in good agreement, certainly within the errors associated with the relevant experiments. However, when Mulliken population analyses are performed, rather different results are obtained from different basis sets and methods, and this emphasizes the difficulty of comparing theoretical atomic orbital populations with those obtained by least-squares modelling of the experimental data.
引用
收藏
页码:1953 / 1959
页数:7
相关论文
共 44 条