Theoretical calculations of effective exchange integrals by spin projected and unprojected broken-symmetry methods.: I.: Cluster models of K2NiF4-type solids

被引:29
作者
Onishi, T [1 ]
Yamaki, D
Yamaguchi, K
Takano, Y
机构
[1] Osaka Univ, Dept Chem, Grad Sch Sci, Osaka 5600043, Japan
[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
D O I
10.1063/1.1567251
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
Previously, various symmetry-adapted (SA) and broken-symmetry (BS) computations have been performed for strongly correlated transition metal species so as to examine magnetic properties in simple cluster models such as binuclear transition metal oxides. Though SA computations such as the complete active space configuration interaction and CASSCF are desirable for estimating physical constants, these computations are heavy for larger cluster models with strongly correlated electrons. K2NiF4 is known to be the two-dimensional perovskite-type antiferromagnet and to have the electronic configuration similar to that of La2CuO4. Here, we have examined the utility and applicability of the BS spin-polarized hybrid-density functional theory (HUDFT) for cluster models of K2NiF4. As the result, HUDFT calculation such as UB2LYP has provided the reasonable effective exchange integral (J(ab)) followed by our approximately spin projected scheme, in comparison to the experimental one. It was also found that the square planar tetranuclear model has provided the most reasonable J(ab) value by HUDFT. In addition, external effects such as putting point charges around cluster models and changing distances between nickel and fluorine have been also examined. The natural orbital analysis by HUDFT has been carried out to obtain natural orbitals and their occupation numbers. Charge density, spin density, and chemical indices expressed by the occupation numbers have been also obtained to elucidate the nature of the chemical bonds in the K2NiF4-type solids. (C) 2003 American Institute of Physics.
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页码:9747 / 9761
页数:15
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