Failure of time-dependent density functional methods for excitations in spatially separated systems

被引:93
作者
Hieringer, W [1 ]
Görling, A [1 ]
机构
[1] Univ Erlangen Nurnberg, Lehrstuhl Theoret Chem, D-91058 Erlangen, Germany
关键词
D O I
10.1016/j.cplett.2005.11.112
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
Time-dependent density-functional methods using present-day exchange-correlation functionals lead to incorrect results for electronic excitations in systems with non-overlapping entities even if there is no net charge-transfer accompanying the excitations. An analysis shows that this problem is caused by shortcomings in the presently available exchange-correlation kernels. As an example, a symmetric ethene dimer model system is considered, and it is demonstrated that the problem leads to artificially low excitation energies not present in an isolated ethene molecule. The problem reported is related to the well-known charge-transfer problem of time-dependent density functional theory, although in the present case no net charge-transfer occurs. (c) 2005 Elsevier B.V. All rights reserved.
引用
收藏
页码:557 / 562
页数:6
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