Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.
Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.
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DOI：
10.1021/acs.jpclett.7b02202
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发表时间：
2017-10-05
期刊：
影响因子：
--
通讯作者：
Gao J
中科院分区：
文献类型：
--
作者：
Grofe A;Chen X;Liu W;Gao J
Kohn-Sham密度泛函理论在化学和物理领域都取得了巨大的成功。然而，它不能用任何近似泛函来描述自旋多重态分量的能量简并。这项工作有两个贡献。(1)提出了一种多态密度泛函理论(MSDFT)来描述自旋多重态成分和确定多重态能量。MSDFT是一种结合了波函数理论和密度泛函理论的混合方法。因此，基态和激发态以及不同组分的波函数、电子密度和能量密度泛函被统一处理。以原子和分子的价激发为例说明了该方法。(2)重要的是，对于可以用Kohn-Sham密度泛函理论分别确定高自旋分量的情况，可以严格定义MSDFT中描述电子耦合的跃迁密度泛函。数值结果可用于设计和优化多组态密度泛函中组态耦合的跃迁密度泛函。
Kohn–Sham density functional theory has been tremendously successful in chemistry and physics. Yet, it is unable to describe the energy degeneracy of spin-multiplet components with any approximate functional. This work features two contributions. (1) We present a multistate density functional theory (MSDFT) to represent spinmultiplet components and to determine multiplet energies. MSDFT is a hybrid approach, taking advantage of both wave function theory and density functional theory. Thus, the wave functions, electron densities and energy density-functionals for ground and excited states and for different components are treated on the same footing. The method is illustrated on valence excitations of atoms and molecules. (2) Importantly, a key result is that for cases in which the high-spin components can be determined separately by Kohn–Sham density functional theory, the transition density functional in MSDFT (which describes electronic coupling) can be defined rigorously. The numerical results may be explored to design and optimize transition density functionals for configuration coupling in multiconfigurational DFT.
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