论文标题

加速使用优化高斯基集的辅助场量子蒙特卡洛少量无脱泌体的收敛性

Accelerating the Convergence of Auxiliary-Field Quantum Monte Carlo inSolids with Optimized Gaussian Basis Sets

论文作者

Morales, Miguel A., Malone, Fionn D.

论文摘要

我们研究了优化相关性一致的高斯基集以研究用辅助场量子蒙特卡洛(AFQMC)进行绝缘固体的研究。通过最小化二阶Møller-Plesset扰动理论(MP2)能量在固体小单元中的二阶Møller-Plesset扰动理论(MP2)能量的最小化来优化基集的指数。我们将文献中提出的其他替代基集进行比较,即以Kohn-Sham的基础和MP2计算的自然轨道进行比较。我们发现,与Kohn-SHAM基础相比,我们的优化基础集可以加快AFQMC相关能量的收敛性,并以与MP2天然轨道相似的收敛,并以产生它们所需的成本的一小部分。我们还建议使用改进的,基于方法的基于MP2的基于集合校正,该校正大大降低了相关能量所需的基集大小。有了这些发展,我们研究了LIH,SI和MGO中这些基础集的相对性能,并确定我们的优化基集将结果最一致的结果作为体积的函数。使用这些优化的基集,我们将AFQMC计算系统地收敛为完整的基集和热力学限制,并与研究系统的实验找到了极好的一致性。尽管我们专注于AFQMC,但我们的基础设定生成过程独立于随后的相关波函数方法。

We investigate the use of optimized correlation consistent gaussian basis sets for the study of insulating solids with auxiliary-field quantum Monte Carlo (AFQMC). The exponents of the basis set are optimized through the minimization of the second order Møller--Plesset perturbation theory (MP2) energy in a small unit cell of the solid. We compare against other alternative basis sets proposed in the literature, namely calculations in the Kohn--Sham basis and in the natural orbitals of an MP2 calculation. We find that our optimized basis sets accelerate the convergence of the AFQMC correlation energy compared to a Kohn--Sham basis, and offer similar convergence to MP2 natural orbitals at a fraction of the cost needed to generate them. We also suggest the use of an improved, method independent, MP2-based basis set correction that significantly reduces the required basis set sizes needed to converge the correlation energy. With these developments, we study the relative performance of these basis sets in LiH, Si and MgO, and determine that our optimized basis sets yield the most consistent results as a function of volume. Using these optimized basis sets, we systematically converge the AFQMC calculations to the complete basis set and thermodynamic limit and find excellent agreement with experiment for systems studied. Although we focus on AFQMC, our basis set generation procedure is independent of the subsequent correlated wavefunction method used.

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