Discretization error cancellation in electronic structure calculation: toward a quantitative study
From MaRDI portal
Estimates of eigenvalues in context of PDEs (35P15) NLS equations (nonlinear Schrödinger equations) (35Q55) Error analysis and interval analysis (65G99) Numerical methods for eigenvalue problems for boundary value problems involving PDEs (65N25) Computational methods for problems pertaining to quantum theory (81-08) Molecular physics (81V55) Software, source code, etc. for problems pertaining to statistical mechanics (82-04)
Abstract: It is often claimed that error cancellation plays an essential role in quantum chemistry and first-principle simulation for condensed matter physics and materials science. Indeed, while the energy of a large, or even medium-size, molecular system cannot be estimated numerically within chemical accuracy (typically 1 kcal/mol or 1 mHa), it is considered that the energy difference between two configurations of the same system can be computed in practice within the desired accuracy. The purpose of this paper is to provide a quantitative study of discretization error cancellation. The latter is the error component due to the fact that the model used in the calculation (e.g. Kohn-Sham LDA) must be discretized in a finite basis set to be solved by a computer. We first report comprehensive numerical simulations performed with Abinit on two simple chemical systems, the hydrogen molecule on the one hand, and a system consisting of two oxygen atoms and four hydrogen atoms on the other hand. We observe that errors on energy differences are indeed significantly smaller than errors on energies, but that these two quantities asymptotically converge at the same rate when the energy cut-off goes to infinity. We then analyze a simple one-dimensional periodic Schr"odinger equation with Dirac potentials, for which analytic solutions are available. This allows us to explain the discretization error cancellation phenomenon on this test case with quantitative mathematical arguments.
Recommendations
- Discretization error cancellation in the plane-wave approximation of periodic Hamiltonians with Coulomb singularities
- Error bars and quadratically convergent methods for the numerical simulation of the Hartree-Fock equations
- Numerical analysis of the planewave discretization of some orbital-free and Kohn-Sham models
- Practical error bounds for properties in plane-wave electronic structure calculations
- scientific article; zbMATH DE number 2152892
Cited in
(4)- Variational projector augmented-wave method: theoretical analysis and preliminary numerical results
- Discretization error cancellation in the plane-wave approximation of periodic Hamiltonians with Coulomb singularities
- Projector augmented-wave method: an analysis in a one-dimensional setting
- Unified analysis of finite-size error for periodic Hartree-Fock and second order Møller-Plesset perturbation theory
This page was built for publication: Discretization error cancellation in electronic structure calculation: toward a quantitative study
Report a bug (only for logged in users!)Click here to report a bug for this page (MaRDI item Q4602357)
