Fukui functions from the relaxed Kohn-Sham orbitals

被引:131
作者
Michalak, A
De Proft, F
Geerlings, P
Nalewajski, RF
机构
[1] Jagiellonian Univ, K Guminski Dept Theoret Chem, PL-30060 Krakow, Poland
[2] Free Univ Brussels, Eenheid Algemene Chem, B-1050 Brussels, Belgium
[3] Jagiellonian Univ, Dept Computat Methods, PL-30060 Krakow, Poland
关键词
D O I
10.1021/jp982761i
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
The global Fukui function of a molecular system, f(r) = (partial derivative rho(r)/partial derivative N)(upsilon), where rho is the ground-state density of a system containing N electrons moving in the external potential upsilon(r), is calculated within a single Kohn-Sham calculation. It is determined by adding to the rigid (frontier orbital) term, relevant for the electron removal (dN < 0) or addition (dN > 0), the density relaxation contribution determined from the N-differentiated Kohn-Sham equations. The only approximation introduced is a neglect of the exchange-correlation terms in the N-derivative of the effective one-body potential. The corresponding equations resulting from the basis set expansion of orbitals are derived, and illustrative results for CO, HCM, H2CO are reported, The predicted Fukui functions for pyrrole, furane, and tiophene are used to diagnose reactivity toward an electrophilic attack. The contour maps of f(r) and the resulting condensed Fukui function indices are compared with the corresponding \Delta N\ = 1 and the "exact" \Delta N\ --> 0 finite difference predictions.
引用
收藏
页码:762 / 771
页数:10
相关论文
共 51 条