基于广义球谐展开的高效分子密度泛函理论
Efficient molecular density functional theory using generalized spherical harmonics expansions
摘要：
我们表明，广义球谐函数是非常适合代表的空间和取向的分子密度的分子密度泛函理论的分辨率。我们考虑的共同系统的任意复杂性的刚性溶质浸泡在分子溶剂中，都表示与相互作用的原子网站和经典力场的分子。溶质周围的分子溶剂密度$ρ(\mathbf{r},\mathbfΩ)$是位置$\mathbf{r}\equiv(x,y,z)$和描述溶剂取向的三个欧拉角$\mathbfΩ\equiv(θ,ϕ,ψ)$的函数。标准密度泛函，相当于HNC封闭的溶质-溶剂的相关性在液体理论中，相对于$ρ(\mathbf{r},\mathbfΩ)$最小化。到目前为止非常昂贵的角卷积乘积有利地由在广义球谐函数上的投影之间的简单乘积代替。分辨率速度的显著提高使得能够以系统的方式探索任意溶剂中高达纳米尺寸的分子溶质，并在最多几分钟内计算其溶剂化自由能和相关的微观溶剂结构。最后，我们说明了形式主义，通过解决各种复杂的分子在水中的溶剂化。
英文摘要：
We show that generalized spherical harmonics are well suited for representing the space and orientation molecular density in the resolution of the molecular density functional theory. We consider the common system made of a rigid solute of arbitrary complexity immersed in a molecular solvent, both represented by molecules with interacting atomic sites and classical force fields. The molecular solvent density $ρ(\mathbf{r},\mathbfΩ)$ around the solute is a function of the position $\mathbf{r}\equiv(x,y,z)$ and of the three Euler angles $\mathbfΩ\equiv(θ,ϕ,ψ)$ describing the solvent orientation. The standard density functional, equivalent to the HNC closure for the solute-solvent correlations in the liquid theory, is minimized with respect to $ρ(\mathbf{r},\mathbfΩ)$. The up-to-now very expensive angular convolution products are advantageously replaced by simple products between projections onto generalized spherical harmonics. The dramatic gain in speed of resolution enables to explore in a systematic way molecular solutes of up to nanometric sizes in arbitrary solvents and to calculate their solvation free energy and associated microscopic solvent structure in at most a few minutes. We finally illustrate the formalism by tackling the solvation of molecules of various complexity in water.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
