论文标题

用于电子结构计算的一般相关双子ansatz:利用PFAFFIAN代替决定因素

General correlated geminal ansatz for electronic structure calculations: exploiting Pfaffians in place of determinants

论文作者

Genovese, Claudio, Shirakawa, Tomonori, Nakano, Kousuke, Sorella, Sandro

论文摘要

我们在这里提出了一个单一的PFAFFIAN相关变异ANSATZ,该变异性ANSATZ极大地提高了相对于单个决定符的准确性,同时以相似的计算成本保持。确实,相关能量确实取决于最通用的两个电子配对函数,包括单重线和三重态通道,结合了多体jastrow因子,包括所有可能的自旋旋转旋转密度和密度密度项。利用这种准确性的主要技术成分是使用Pfaffian对高度相关的配对函数进行反对称,从而恢复了具有负担得起的计算成本的电子统计数据。此外,在固定节点近似中,扩散蒙特卡洛的应用使我们能够为本研究报告的第一个初步计算获得非常准确的结合能:c $ _2 $,n $ _2 $和o $ _2 $和苯苯基分子。考虑到它们代表了非常困难的分子,即使对于计算要求的多确定方法,这是非常有希望的,而且非常出色,因此为实现算法缩放的算法作为电子数量的第四强度,为现实,准确的电子仿真开辟了道路。

We propose here a single Pfaffian correlated variational ansatz, that dramatically improves the accuracy with respect to the single determinant one, while remaining at a similar computational cost. A much larger correlation energy is indeed determined by the most general two electron pairing function, including both singlet and triplet channels, combined with a many-body Jastrow factor, including all possible spin-spin spin-density and density-density terms. The main technical ingredient to exploit this accuracy is the use of the Pfaffian for antisymmetrizing an highly correlated pairing function, thus recovering the Fermi statistics for electrons with an affordable computational cost. Moreover the application of the Diffusion Monte Carlo, within the fixed node approximation, allows us to obtain very accurate binding energies for the first preliminary calculations reported in this study: C$_2$, N$_2$ and O$_2$ and the benzene molecule. This is promising and remarkable, considering that they represent extremely difficult molecules even for computationally demanding multi-determinant approaches, and opens therefore the way for realistic and accurate electronic simulations with an algorithm scaling at most as the fourth power of the number of electrons.

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