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arXiv 2602.14923physics.comp-phphysics.chem-ph
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辅助场量子蒙特卡洛方法在基组极限下的应用:用于晶格常数的计算

Auxiliary field quantum Monte Carlo at the basis set limit: application to lattice constants

University of Vienna(维也纳大学);VASP Software GmbH(VASP软件有限公司);Institute for Theoretical Physics, TU Wien(维也纳工业大学理论物理研究所)

Moritz Humer, Martin Schlipf, Zoran Sukurma, Sajad Bazrafshan, Georg Kresse

AI总结:

本文提出基于平面波的辅助场量子蒙特卡洛方法,在完整基组极限下计算晶格常数,验证了其在结构性质评估中的高精度和可靠性。

摘要:

我们展示了在维也纳初始化模拟包(VASP)中的投影增强波(PAW)形式下,平面波(PW)实现的辅助场量子蒙特卡洛(AFQMC)方法。通过采用PAW重叠算子的精确反演,我们的方法在保持立方标度的同时,自然地在由PW截止定义的完整基组极限下运行。我们通过计算C、BN、BP和Si的平衡晶格常数和体积模量来验证这一框架。我们的分析表明,AFQMC系统性地纠正了MP2中长程筛选不足和RPA中缺失的高阶交换。我们确定RPA为最优参考方法,因为剩余的短程相关性随着超晶格尺寸迅速收敛。所得到的晶格常数相对于实验的平均绝对相对误差为0.14%,证明了该方法作为凝聚物质系统结构性质的严格基准工具。

英文摘要:

We present a plane-wave (PW) implementation of the auxiliary-field quantum Monte Carlo (AFQMC) method within the projector augmented-wave (PAW) formalism in the Vienna ab initio Simulation Package (VASP). By employing an exact inversion of the PAW overlap operator, our approach maintains cubic scaling while naturally operating at the complete basis set limit defined by the PW cutoff. We benchmark this framework by calculating the equilibrium lattice constants and bulk moduli of C, BN, BP, and Si. Our analysis demonstrates that AFQMC systematically corrects the lack of long-range screening in MP2 and the missing higher-order exchange in RPA. We identify RPA as the optimal reference method due to the rapid convergence of the remaining short-range correlations with respect to supercell size. The resulting lattice constants exhibit a mean absolute relative error of 0.14 % relative to experiment, establishing the method as a rigorous benchmark tool for structural properties in condensed matter systems.

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