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首页> 外文期刊>The Journal of Chemical Physics >Dispersion interactions in density-functional theory: An adiabatic-connection analysis
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Dispersion interactions in density-functional theory: An adiabatic-connection analysis

机译:密度泛函理论中的色散相互作用:绝热连接分析

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摘要

We present an analysis of the dispersion interaction energy and forces in density-functional theory from the point of view of the adiabatic connection between the Kohn-Sham non-interacting and fully interacting systems. Accurate coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] densities are computed for the helium dimer and used to construct the exchange-correlation potential of Kohn-Sham theory, showing agreement with earlier results presented for the Hartree-Fock-Kohn-Sham method [M. Allen and D. J. Tozer, J. Chem. Phys. 117, 11113 (2002)10.1063/1.1522715]. The accuracy of the methodology utilized to determine these solutions is checked by calculation of the Hellmann-Feynman forces based on the Kohn-Sham densities, which are compared with analytic CCSD(T) forces. To ensure that this comparison is valid in a finite atomic-orbital basis set, we employ floating Gaussian basis functions throughout and all results are counterpoise corrected. The subtle charge-rearrangement effects associated with the dispersion interaction are highlighted as the origin of a large part of the dispersion force. To recover the exchange-correlation components of the interaction energy, adiabatic connections are constructed for the supermolecular system and for its constituent atoms; subtraction of the resulting adiabatic-connection curves followed by integration over the interaction strength recovers the exchange-correlation contribution relevant to the density-functional description of the dispersion interaction. The results emphasize the long-ranged, dynamically correlated nature of the dispersion interaction between closed-shell species. An alternative adiabatic-connection path is also explored, where the electronic interactions are introduced in a manner that emphasizes the range of the electronic interactions, highlighting their purely long-ranged nature, consistent with the success of range-separated hybrid approaches in this context.
机译:我们从Kohn-Sham非相互作用系统和完全相互作用系统之间的绝热连接的角度,对密度泛函理论中的色散相互作用能和力进行了分析。计算氦二聚体的精确耦合簇单重-双扰动三重[CCSD(T)]密度,并用于构建Kohn-Sham理论的交换相关势,表明与先前针对Hartree-Fock提出的结果一致-Kohn-Sham方法[M. Allen和D.J. Tozer,J.Chem。物理117,11113(2002)10.1063 / 1.1522715]。通过基于Kohn-Sham密度的Hellmann-Feynman力的计算来检查用于确定这些解决方案的方法的准确性,并将其与CCSD(T)解析力进行比较。为确保此比较在有限的原子轨道基集中有效,我们始终采用浮动高斯基函数,并且所有结果都经过了平衡修正。与色散相互作用相关的微妙的电荷重排效应被突出为大部分色散力的起源。为了恢复相互作用能的交换相关分量,为超分子系统及其组成原子构建了绝热连接。减去最终的绝热连接曲线,然后在相互作用强度上进行积分,可得到与色散相互作用的密度泛函相关的交换相关贡献。结果强调了封闭壳物种之间的分散相互作用的远程动态关联性质。还探索了另一种绝热连接路径,其中以强调电子交互作用的范围,突出其纯远距离性质的方式引入了电子交互作用,这与这种情况下范围分离的混合方法的成功相一致。

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