Annarelli Alfonso, Alfè Dario, Zen Andrea
Dipartimento di Fisica Ettore Pancini, Università di Napoli Federico II, Monte S. Angelo, I-80126 Napoli, Italy.
Department of Earth Sciences, University College London, Gower Street, London WC1E 6BT, United Kingdom.
J Chem Phys. 2024 Dec 28;161(24). doi: 10.1063/5.0232424.
Quantum Monte Carlo (QMC) methods represent a powerful family of computational techniques for tackling complex quantum many-body problems and performing calculations of stationary state properties. QMC is among the most accurate and powerful approaches to the study of electronic structure, but its application is often hindered by a steep learning curve; hence it is rarely addressed in undergraduate and postgraduate classes. This tutorial is a step toward filling this gap. We offer an introduction to the diffusion Monte Carlo (DMC) method, which aims to solve the imaginary time Schrödinger equation through stochastic sampling of the configuration space. Starting from the theoretical foundations, the discussion leads naturally to the formulation of a step-by-step algorithm. To illustrate how the method works in simplified scenarios, examples such as the harmonic oscillator and the hydrogen atom are provided. The discussion extends to the fixed-node approximation, a crucial approach for addressing the fermionic sign problem in multi-electron systems. In particular, we examine the influence of trial wave function nodal surfaces on the accuracy of DMC energy by evaluating results from a non-interacting two-fermion system. Extending the method to excited states is feasible in principle, but some additional considerations are needed, supported by practical insights. By addressing the fundamental concepts from a hands-on perspective, we hope this tutorial will serve as a valuable guide for researchers and students approaching DMC for the first time.
量子蒙特卡罗(QMC)方法是用于解决复杂量子多体问题和计算稳态性质的一类强大的计算技术。QMC是研究电子结构最精确、最强大的方法之一,但其应用常常因学习曲线陡峭而受阻;因此,本科和研究生课程中很少涉及。本教程旨在填补这一空白。我们介绍扩散蒙特卡罗(DMC)方法,该方法旨在通过对构型空间进行随机采样来求解虚时薛定谔方程。从理论基础出发,讨论自然地引出了逐步算法的制定。为了说明该方法在简化场景中的工作原理,提供了诸如谐振子和氢原子等示例。讨论扩展到固定节点近似,这是解决多电子系统中费米子符号问题的关键方法。特别是,我们通过评估非相互作用双费米子系统的结果,研究了试探波函数节点面对DMC能量精度的影响。原则上,将该方法扩展到激发态是可行的,但需要一些额外的考虑,并辅以实际见解。通过从实践的角度阐述基本概念,我们希望本教程能为首次接触DMC的研究人员和学生提供有价值的指导。