基于冻结密度嵌入理论的实验电子密度模拟
Frozen-Density Embedding Theory based simulations with experimental electron densities
摘要：
冻结密度嵌入理论（FDET）的基本思想是使用辅助泛函$E_{v_{AB}}^{FDET}[Ψ_A,ρ_B]$执行的Hohenberg-Kohn密度泛函$E^{HK}[ρ]$的约束最小化，其中$Ψ_A$是嵌入的$N_A$ -电子波函数，而$ρ_B(\vec{\mathrm{r}})$是实空间中积分到给定数量的电子$N_B$的非负函数。在总能量泛函$E_{v_{AB}}^{FDET}[Ψ_A,ρ_B]$中独立变量的这种选择使得在多级模拟中使用不同的方法来处理总密度的相应两个分量成为可能。我们证明，第一次，FDET使用$ρ_B(\vec{\mathrm{r}})$重建从X射线衍射数据的分子晶体上的应用。对于涉及发色团（用$Ψ_A$表示）和甘氨酰甘氨酸分子（用$ρ_B(\vec{\mathrm{r}})$表示）的八个氢键簇，FDET用于导出激发能。结果表明，实验密度是适合被用作$ρ_B(\vec{\mathrm{r}})$在FDET为基础的模拟。
英文摘要：
The basic idea of Frozen-Density Embedding Theory (FDET) is the constrained minimisation of the Hohenberg-Kohn density functional $E^{HK}[ρ]$ performed using the auxiliary functional $E_{v_{AB}}^{FDET}[Ψ_A,ρ_B]$, where $Ψ_A$ is the embedded $N_A$-electron wave-function and $ρ_B(\vec{\mathrm{r}})$ a non-negative function in real space integrating to a given number of electrons $N_B$. This choice of independent variables in the total energy functional $E_{v_{AB}}^{FDET}[Ψ_A,ρ_B]$ makes it possible to treat the corresponding two components of the total density using different methods in multi-level simulations. We demonstrate, for the first time, the applications of FDET using $ρ_B(\vec{\mathrm{r}})$ reconstructed from X-ray diffraction data on a molecular crystal. For eight hydrogen-bonded clusters involving a chromophore (represented with $Ψ_A$) and the glycylglycine molecule (represented as $ρ_B(\vec{\mathrm{r}})$), FDET is used to derive excitation energies. It is shown that experimental densities are suitable to be used as $ρ_B(\vec{\mathrm{r}})$ in FDET based simulations.
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