Eric Cancès

Eric Cancès, Rachida Chakir, Yvon Maday

We provide a priori error estimates for the spectral and pseudospectral Fourier (also called planewave) discretizations of the periodic Thomas-Fermi-von Weizsäcker (TFW) model and for the spectral discretization of the Kohn-Sham model, within the local density approximation (LDA). These models allow to compute approximations of the ground state energy and density of molecular systems in the condensed phase. The TFW model is stricly convex with respect to the electronic density, and allows for a comprehensive analysis. This is not the case for the Kohn-Sham LDA model, for which the uniqueness of the ground state electronic density is not guaranteed. Under a coercivity assumption on the second order optimality condition, we prove that for large enough energy cut-offs, the discretized Kohn-Sham LDA problem has a minimizer in the vicinity of any Kohn-Sham ground state, and that this minimizer is unique up to unitary transform. We then derive optimal a priori error estimates for the spectral discretization method.

Xavier Blanc, Eric Cancès, Mi-Song Dupuy

In Kohn-Sham electronic structure computations, wave functions have singularities at nuclear positions. Because of these singularities, plane-wave expansions give a poor approximation of the eigenfunctions. In conjunction with the use of pseudo-potentials, the PAW (projector augmented-wave) method circumvents this issue by replacing the original eigenvalue problem by a new one with the same eigenvalues but smoother eigenvectors. Here a slightly different method, called VPAW (variational PAW), is proposed and analyzed. This new method allows for a better convergence with respect to the number of plane-waves. Some numerical tests on an idealized case corroborate this efficiency.

Eric Cancès, Geneviève Dusson

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 Schrödinger 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.

Eric Cancès, Virginie Ehrlacher, Frederic Legoll et al.

This contribution is the numerically oriented companion article of the work [E. Cancès, V. Ehrlacher, F. Legoll, B. Stamm and S. Xiang, arxiv preprint 1807.05131]. We focus here on the numerical resolution of the embedded corrector problem introduced in [E. Cancès, V. Ehrlacher, F. Legoll and B. Stamm, CRAS 2015; E. Cancès, V. Ehrlacher, F. Legoll, B. Stamm and S. Xiang, arxiv preprint 1807.05131] in the context of homogenization of diffusion equations. Our approach consists in considering a corrector-type problem, posed on the whole space, but with a diffusion matrix which is constant outside some bounded domain. In [E. Cancès, V. Ehrlacher, F. Legoll, B. Stamm and S. Xiang, arxiv preprint 1807.05131], we have shown how to define three approximate homogenized diffusion coefficients on the basis of the embedded corrector problems. We have also proved that these approximations all converge to the exact homogenized coefficients when the size of the bounded domain increases. We show here that, under the assumption that the diffusion matrix is piecewise constant, the corrector problem to solve can be recast as an integral equation. In case of spherical inclusions with isotropic materials, we explain how to efficiently discretize this integral equation using spherical harmonics, and how to use the fast multipole method (FMM) to compute the resulting matrix-vector products at a cost which scales only linearly with respect to the number of inclusions. Numerical tests illustrate the performance of our approach in various settings.

Eric Cancès, Virginie Ehrlacher, Frederic Legoll et al.

This article is the first part of a two-fold study, the objective of which is the theoretical analysis and numerical investigation of new approximate corrector problems in the context of stochastic homogenization. We present here three new alternatives for the approximation of the homogenized matrix for diffusion problems with highly-oscillatory coefficients. These different approximations all rely on the use of an embedded corrector problem (that we previously introduced in [Cancès, Ehrlacher, Legoll and Stamm, C. R. Acad. Sci. Paris, 2015]), where a finite-size domain made of the highly oscillatory material is embedded in a homogeneous infinite medium whose diffusion coefficients have to be appropriately determined. The motivation for considering such embedded corrector problems is made clear in the companion article [Cancès, Ehrlacher, Legoll, Stamm and Xiang, in preparation], where a very efficient algorithm is presented for the resolution of such problems for particular heterogeneous materials. In the present article, we prove that the three different approximations we introduce converge to the homogenized matrix of the medium when the size of the embedded domain goes to infinity.

Eric Cancès, Rachida Chakir, Yvon Maday

We provide {\it a priori} error estimates for the spectral and pseudospectral Fourier (also called planewave) discretizations of the periodic Thomas-Fermi-von Weizsäcker (TFW) model and of the Kohn-Sham model, within the local density approximation (LDA). These models allow to compute approximations of the ground state energy and density of molecular systems in the condensed phase. The TFW model is stricly convex with respect to the electronic density, and allows for a comprehensive analysis (Part I). This is not the case for the Kohn-Sham LDA model, for which the uniqueness of the ground state electronic density is not guaranteed. Under a coercivity assumption on the second order optimality condition, we prove in Part II that for large enough energy cut-offs, the discretized Kohn-Sham LDA problem has a minimizer in the vicinity of any Kohn-Sham ground state, and that this minimizer is unique up to unitary transform. We then derive optimal {\it a priori} error estimates for both the spectral and the pseudospectral discretization methods.

Eric Cancès, Rachida Chakir, Yvon Maday

We provide a priori error estimates for variational approximations of the ground state eigenvalue and eigenvector of nonlinear elliptic eigenvalue problems of the form $-{div} (A\nabla u) + Vu + f(u^2) u = λu$, $\|u\|_{L^2}=1$. We focus in particular on the Fourier spectral approximation (for periodic problems) and on the $¶_1$ and $¶_2$ finite-element discretizations. Denoting by $(u_δ,λ_δ)$ a variational approximation of the ground state eigenpair $(u,λ)$, we are interested in the convergence rates of $\|u_δ-u\|_{H^1}$, $\|u_δ-u\|_{L^2}$ and $|λ_δ-λ|$, when the discretization parameter $δ$ goes to zero. We prove that if $A$, $V$ and $f$ satisfy certain conditions, $|λ_δ-λ|$ goes to zero as $\|u_δ-u\|_{H^1}^2+\|u_δ-u\|_{L^2}$. We also show that under more restrictive assumptions on $A$, $V$ and $f$, $|λ_δ-λ|$ converges to zero as $\|u_δ-u\|_{H^1}^2$, thus recovering a standard result for {\em linear} elliptic eigenvalue problems. For the latter analysis, we make use of estimates of the error $u_δ-u$ in negative Sobolev norms.