Unified analysis of finite-size error for periodic Hartree-Fock and second order Møller-Plesset perturbation theory

DOI10.1090/MCOM/3877arXiv2108.00206OpenAlexW3192946243MaRDI QIDQ6140844FDOQ6140844

Authors: Xin Xing, Xiaoxu Li, Lin Lin 

Publication date: 2 January 2024

Published in: Mathematics of Computation (Search for Journal in Brave)

Abstract: Despite decades of practice, finite-size errors in many widely used electronic structure theories for periodic systems remain poorly understood. For periodic systems using a general Monkhorst-Pack grid, there has been no rigorous analysis of the finite-size error in the Hartree-Fock theory (HF) and the second order M{o}ller-Plesset perturbation theory (MP2), which are the simplest wavefunction based method, and the simplest post-Hartree-Fock method, respectively. Such calculations can be viewed as a multi-dimensional integral discretized with certain trapezoidal rules. Due to the Coulomb singularity, the integrand has many points of discontinuity in general, and standard error analysis based on the Euler-Maclaurin formula gives overly pessimistic results. The lack of analytic understanding of finite-size errors also impedes the development of effective finite-size correction schemes. We propose a unified method to obtain sharp convergence rates of finite-size errors for the periodic HF and MP2 theories. Our main technical advancement is a generalization of the result of [Lyness, 1976] for obtaining sharp convergence rates of the trapezoidal rule for a class of non-smooth integrands. Our result is applicable to three-dimensional bulk systems as well as low dimensional systems (such as nanowires and 2D materials). Our unified analysis also allows us to prove the effectiveness of the Madelung-constant correction to the Fock exchange energy, and the effectiveness of a recently proposed staggered mesh method for periodic MP2 calculations [Xing, Li, Lin, 2021]. Our analysis connects the effectiveness of the staggered mesh method with integrands with removable singularities, and suggests a new staggered mesh method for reducing finite-size errors of periodic HF calculations.

Full work available at URL: https://arxiv.org/abs/2108.00206

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zbMATH Keywords

Hartree-Fockperiodic systemsfinite-size errorMP2 perturbation theory

Mathematics Subject Classification ID

Perturbations in context of PDEs (35B20) Discrete version of topics in analysis (39A12) Error bounds for initial value and initial-boundary value problems involving PDEs (65M15) Yang-Mills and other gauge theories in mechanics of particles and systems (70S15) Computational stability and error-correcting codes for quantum computation and communication processing (81P73) Fixed points and periodic points of finite-dimensional Hamiltonian and Lagrangian systems (37J12)

Cites Work

• The exponentially convergent trapezoidal rule
• Electronic Structure
• Correlation Energy of an Electron Gas at High Density
• A trapezoidal rule error bound unifying the Euler–Maclaurin formula and geometric convergence for periodic functions
• A scalable and accurate algorithm for the computation of Hartree-Fock exchange
• An Error Functional Expansion for N-Dimensional Quadrature with an Integrand Function Singular at a Point
• On the remainder term in the N-dimensional Euler Maclaurin expansion
• Optimal decay of Wannier functions in Chern and quantum Hall insulators
• Asymptotic Expansions for Integration Formulas in One or More Dimensions
• Numerical quadrature in the Brillouin zone for periodic Schrödinger operators

Cited In (1)

• Finite-size effects in periodic coupled cluster calculations

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