论文标题
从第一原理对范围分离的混合功能的自洽系统优化
A self-consistent systematic optimization of range-separated hybrid functionals from first principles
论文作者
论文摘要
在此通信中,我们代表了从\ emph {First Practionles}开发最佳调整(OT)分隔式混合(RSH)功能的自洽系统优化过程。这是我们最近工作的分支,该工作采用了纯数值方法来通过范围分离(RS)技术有效地计算常规全球混合功能中的精确交换贡献。我们利用基于大小的ansatz,即rs参数,$γ$,是密度的函数,$ρ(\ mathbf {r})$,其中知之甚少。为了与此ANSATZ一致,提出了一个新的过程,该过程将给定系统的特征长度(其中$ρ(\ Mathbf {r})$指数衰减至零)与$γ$通过简单的数学约束自我依靠。实际上,$γ_ {\ mathrm {ot}} $是通过优化总能量来获得的,如下所示:$γ_ {\ mathrm {ot}} \ equiv \ equiv \ equiv \ underSet {γ} {γ} {\ mathrm {opt}}}}}} \ e}发现参数$γ_ {\ mathrm {ot}} $,如上所述,在预测属性(尤其是来自边境轨道能量的)中,比给定系统的传统相应的RSH功能可以显示出更好的性能。我们已经检查了从精确的线性行为中占据最高分数占据轨道的性质,这表明这种方法足以维持这种情况。然后,仔细的统计分析说明了当前方法的可行性和适用性。所有计算均在基于笛卡尔网格的伪电势(G)KS-DFT框架中完成。
In this communication, we represent a self-consistent systematic optimization procedure for the development of optimally tuned (OT) range-separated hybrid (RSH) functionals from \emph{first principles}. This is an offshoot of our recent work, which employed a purely numerical approach for efficient computation of exact exchange contribution in the conventional global hybrid functionals through a range-separated (RS) technique. We make use of the size-dependency based ansatz i.e., RS parameter, $γ$, is a functional of density, $ρ(\mathbf{r})$, of which not much is known. To be consistent with this ansatz, a novel procedure is presented that relates the characteristic length of a given system (where $ρ(\mathbf{r})$ exponentially decays to zero) with $γ$ self-consistently via a simple mathematical constraint. In practice, $γ_{\mathrm{OT}}$ is obtained through an optimization of total energy as follows: $γ_{\mathrm{OT}} \equiv \underset{γ}{\mathrm{opt}} \ E_{\mathrm{tot},γ}$. It is found that the parameter $γ_{\mathrm{OT}}$, estimated as above can show better performance in predicting properties (especially from frontier orbital energies) than conventional respective RSH functionals, of a given system. We have examined the nature of highest fractionally occupied orbital from exact piece-wise linearity behavior, which reveals that this approach is sufficient to maintain this condition. A careful statistical analysis then illustrates the viability and suitability of the current approach. All the calculations are done in a Cartesian-grid based pseudopotential (G)KS-DFT framework.