论文标题

冷冻密度嵌入以在Dirac-Kohn-Sham理论中包括环境影响:基于密度拟合和原型技术的实现

Frozen-Density Embedding for including environmental effects in the Dirac-Kohn-Sham theory: an implementation based on density fitting and prototyping techniques

论文作者

De Santis, Matteo, Sorbelli, Diego, Vallet, Valerie, Gomes, Andre' Severo Pereira, Storchi, Loriano, Belpassi, Leonardo

论文摘要

冷冻密度嵌入方案代表了一种嵌入方法,其中通过其电子密度来代表机械构成周围环境的其他子系统来包括在给定子系中的环境效应。在本文中,我们扩展了Bertha代码中实施的完整的4件相对论Dirac-Kohn-Sham方法,以通过FDE方案包括环境和限制效应。 Bertha的Python API(Pybertha)极大地促进了这种实现,该框架通过在代码可重复使用方面使用所有Python优势,同时促进与其他FDE实现的互操作性,从而提供了灵活的开发框架,可以通过PyADF框架提供。已经对一系列金簇(Au $ _n $,n = 2,4,8)评估了计算性能,嵌入了越来越多的水分子(5、10、20、40和80水分子)中。我们发现,该过程与周围环境的尺寸(与FDE方法的基础相一致)和活动系统的大小(与使用密度拟合的使用一致)。最后,我们将代码应用于嵌入在C_60笼中的一系列重型(RN)和超重元素(CN,FL,OG),以探索C_60对其电子结构引起的限制效应。我们将模拟的结果与原子理文献中采用的更多近似模型进行了比较,在原子物理学文献中,限制是由径向电位略微受中央原子本质影响的径向电位所代表的。我们的结果表明,FDE所描述的特定相互作用能够改善当前使用的CRUDER近似值,因此提供了一个基础,从而为封闭原子产生更真实的径向电势。

The Frozen Density Embedding scheme represents an embedding method in which environmental effects onto a given subsystem are included by representing the other subsystems making up the surroundings quantum mechanically, by means of their electron densities. In the present paper, we extend the full 4-component relativistic Dirac-Kohn-Sham method, as implemented in the BERTHA code, to include environmental and confinement effects with the FDE scheme. This implementation has been enormously facilitated by BERTHA's python API (PyBERTHA), which provides a flexible framework of development by using all Python advantages in terms of code re-usability, portability while facilitating the interoperability with other FDE implementations available through the PyADF framework. The computational performance has been evaluated on a series of gold clusters (Au$_n$, with n=2,4,8) embedded into an increasing number of water molecules (5, 10, 20, 40 and 80 water molecules). We found that the procedure scales approximately linearly both with the size of the frozen surrounding environment (in line with the underpinnings of the FDE approach) and with the size of the active system (in line with the use of density fitting). Finally, we applied the code to a series of Heavy (Rn) and Super-Heavy elements (Cn, Fl, Og) embedded in a C_60 cage to explore the confinement effect induced by C_60 on their electronic structure. We compare the results from our simulations with more approximate models employed in the atomic physics literature, in which confinement is represented by a radial potential slightly affected by the nature of the central atom. Our results indicate that the specific interactions described by FDE are able to improve upon the cruder approximations currently employed, and thus provide a basis from which to generate more realistic radial potentials for confined atoms.

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