arXiv subjects
Publications and source records attributed to Gero Friesecke.
We prove the statement in the title, for a suitable (wavefunction-dependent) choice of the underlying orbitals, and show that Three is optimal. Thus for two-electron systems, the QC-DMRG method with bond dimension Three combined with fermionic mode optimization exactly recovers the FCI energy.
We present a novel analogue for finite exchangeable sequences of the de Finetti, Hewitt and Savage theorem and investigate its implications for multi-marginal optimal transport (MMOT) and Bayesian statistics. If $(Z_1,...,Z_N)$ is a finitely exchangeable sequence of $N$ random variables taking values in some Polish space $X$, we show that the law $μ_k$ of the first $k$ components has a representation of the form $μ_k=\int_{{\mathcal P}_{\frac{1}{N}}(X)} F_{N,k}(λ) \, \mbox{d} α(λ)$ for some probability measure $α$ on the set of $1/N$-quantized probability measures on $X$ and certain universal polynomials $F_{N,k}$. The latter consist of a leading term $N^{k-1}\! /{\small \prod_{j=1}^{k-1}(N\! -\! j)\, λ^{\otimes k}}$ and a finite, exponentially decaying series of correlated corrections of order $N^{-j}$ ($j=1,...,k$). The $F_{N,k}(λ)$ are precisely the extremal such laws, expressed via an explicit polynomial formula in terms of their one-point marginals $λ$. Applications include novel approximations of MMOT via polynomial convexification and the identification of the remainder which is estimated in the celebrated error bound of Diaconis-Freedman between finite and infinite exchangeable laws.
We present an example of an electronic wavefunction with maximally entangled MPS representation, in the sense that the bond dimension is maximal and cannot be lowered by any re-ordering of the underlying one-body basis. Our construction works for any number of electrons and orbitals.
We introduce a simple, accurate, and extremely efficient method for numerically solving the multi-marginal optimal transport (MMOT) problems arising in density functional theory. The method relies on (i) the sparsity of optimal plans [for $N$ marginals discretized by $\ell$ gridpoints each, general Kantorovich plans require $\ell^N$ gridpoints but the support of optimizers is of size $O(\ell\cdot N)$ [FV18]], (ii) the method of column generation (CG) from discrete optimization which to our knowledge has not hitherto been used in MMOT, and (iii) ideas from machine learning. The well-known bottleneck in CG consists in generating new candidate columns efficiently; we prove that in our context, finding the best new column is an NP-complete problem. To overcome this bottleneck we use a genetic learning method tailormade for MMOT in which the dual state within CG plays the role of an "adversary", in loose similarity to Wasserstein GANs. On a sequence of benchmark problems with up to 120 gridpoints and up to 30 marginals, our method always found the exact optimizers. Moreover, empirically the number of computational steps needed to find them appears to scale only polynomially when both $N$ and $\ell$ are simultaneously increased (while keeping their ratio fixed to mimic a thermodynamic limit of the particle system).
We study the barycenter of the Hellinger--Kantorovich metric over non-negative measures on compact, convex subsets of $\mathbb{R}^d$. The article establishes existence, uniqueness (under suitable assumptions) and equivalence between a coupled-two-marginal and a multi-marginal formulation. We analyze the HK barycenter between Dirac measures in detail, and find that it differs substantially from the Wasserstein barycenter by exhibiting a local `clustering' behaviour, depending on the length scale of the input measures. In applications it makes sense to simultaneously consider all choices of this scale, leading to a 1-parameter family of barycenters. We demonstrate the usefulness of this family by analyzing point clouds sampled from a mixture of Gaussians and inferring the number and location of the underlying Gaussians.
The tensor train approximation of electronic wave functions lies at the core of the QC-DMRG (Quantum Chemistry Density Matrix Renormalization Group) method, a recent state-of-the-art method for numerically solving the $N$-electron Schrödinger equation. It is well known that the accuracy of TT approximations is governed by the tail of the associated singular values, which in turn strongly depends on the ordering of the one-body basis. Here we find that the singular values $s_1\ge s_2\ge ... \ge s_d$ of tensors representing ground states of noninteracting Hamiltonians possess a surprising inversion symmetry, $s_1s_d=s_2s_{d-1}=s_3s_{d-2}=...$, thus reducing the tail behaviour to a single hidden invariant, which moreover depends explicitly on the ordering of the basis. For correlated wavefunctions, we find that the tail is upper bounded by a suitable superposition of the invariants. Optimizing the invariants or their superposition thus provides a new ordering scheme for QC-DMRG. Numerical tests on simple examples, i.e. linear combinations of a few Slater determinants, show that the new scheme reduces the tail of the singular values by several orders of magnitudes over existing methods, including the widely used Fiedler order.
In numerical computations of response properties of electronic systems, the standard model is Kohn-Sham density functional theory (KS-DFT). Here we investigate the mathematical status of the simplest class of excitations in KS-DFT, HOMO-LUMO excitations. We show using concentration-compactness arguments that such excitations, i.e. excited states of the Kohn-Sham Hamiltonian, exist for $Z>N$, where $Z$ is the total nuclear charge and $N$ is the number of electrons. The result applies under realistic assumptions on the exchange-correlation functional, which we verify explicitly for the widely used PZ81 and PW92 functionals. By contrast, and somewhat surprisingly, we find using a method of Glaser, Martin, Grosse, and Thirring \cite{glaser1976} that in case of the hydrogen and helium atoms, excited states do not exist in the neutral case $Z=N$ when the self-consistent KS ground state density is replaced by a realistic but easier to analyze approximation (in case of hydrogen, the true Schrödinger ground state density). Implications for interpreting minus the HOMO eigenvalue as an approximation to the ionization potential are indicated.
We present and study novel optimal control problems motivated by the search for photovoltaic materials with high power-conversion efficiency. The material must perform the first step: convert light (photons) into electronic excitations. We formulate various desirable properties of the excitations as mathematical control goals at the Kohn-Sham-DFT level of theory, with the control being given by the nuclear charge distribution. We prove that nuclear distributions exist which give rise to optimal HOMO-LUMO excitations, and present illustrative numerical simulations for 1D finite nanocrystals. We observe pronounced goal-dependent features such as large electron-hole separation, and a hierarchy of length scales: internal HOMO and LUMO wavelengths $<$ atomic spacings $<$ (irregular) fluctuations of the doping profiles $<$ system size.
It is known from clever mathematical examples \cite{Ca10} that the Monge ansatz may fail in continuous two-marginal optimal transport (alias optimal coupling alias optimal assignment) problems. Here we show that this effect already occurs for finite assignment problems with $N=3$ marginals, $\ell=3$ 'sites', and symmetric pairwise costs, with the values for $N$ and $\ell$ both being optimal. Our counterexample is a transparent consequence of the convex geometry of the set of symmetric Kantorovich plans for $N=\ell=3$, which -- as we show -- possess 22 extreme points, only 7 of which are Monge. These extreme points have a simple physical meaning as irreducible molecular packings, and the example corresponds to finding the minimum energy packing for Frenkel-Kontorova interactions. Our finite example naturally gives rise, by superposition, to a continuous one, where failure of the Monge ansatz manifests itself as nonattainment and formation of 'microstructure'.
We prove rigorously that the exact N-electron Hohenberg-Kohn density functional converges in the strongly interacting limit to the strictly correlated electrons (SCE) functional, and that the absolute value squared of the associated constrained-search wavefunction tends weakly in the sense of probability measures to a minimizer of the multi-marginal optimal transport problem with Coulomb cost associated to the SCE functional. This extends our previous work for N=2 [CFK11]. The correct limit problem has been derived in the physics literature by Seidl [Se99] and Seidl, Gori-Giorgi and Savin [SGS07]; in these papers the lack of a rigorous proof was pointed out. We also give a mathematical counterexample to this type of result, by replacing the constraint of given one-body density -- an infinite-dimensional quadratic expression in the wavefunction -- by an infinite-dimensional quadratic expression in the wavefunction and its gradient. Connections with the Lawrentiev phenomenon in the calculus of variations are indicated.
We show that minimizers of the Heitmann-Radin energy (R. C. Heitmann, C. Radin, J. Stat. Phys. 22, 281-287, 1980) are unique if and only if the particle number N belongs to an infinite sequence whose first thirty-five elements are 1, 2, 3, 4, 5, 7, 8, 10, 12, 14, 16, 19, 21, 24, 27, 30, 33, 37, 40, 44, 48, 52, 56, 61, 65, 70, 75, 80, 85, 91, 96, 102, 108, 114, 120 (see the paper for a closed-form description of this sequence). The proof relies on the discrete differential geometry techniques introduced in (L. De Luca, G. Friesecke, preprint).
A new class of cost functionals for optimal control of quantum systems which produces controls which are sparse in frequency and smooth in time is proposed. This is achieved by penalizing a suitable time-frequency representation of the control field, rather than the control field itself, and by employing norms which are of $L^1$ or measure form with respect to frequency but smooth with respect to time. We prove existence of optimal controls for the resulting nonsmooth optimization problem, derive necessary optimality conditions, and rigorously establish the frequency-sparsity of the optimizers. More precisely, we show that the time-frequency representation of the control field, which a priori admits a continuum of frequencies, is supported on only \textit{ finitely many} frequencies. These results cover important systems of physical interest, including (infinite-dimensional) Schrödinger dynamics on multiple potential energy surfaces as arising in laser control of chemical reactions. Numerical simulations confirm that the optimal controls, unlike those obtained with the usual $L^2$ costs, concentrate on just a few frequencies, even in the infinite-dimensional case of laser-controlled chemical reactions.
We show that the emerging field of discrete differential geometry can be usefully brought to bear on crystallization problems. In particular, we give a simplified proof of the Heitmann-Radin crystallization theorem (R. C. Heitmann, C. Radin, J. Stat. Phys. 22, 281-287, 1980), which concerns a system of $N$ identical atoms in two dimensions interacting via the idealized pair potential $V(r)=+\infty$ if $r<1$, $-1$ if $r=1$, $0$ if $r>1$. This is done by endowing the bond graph of a general particle configuration with a suitable notion of {\it discrete curvature}, and appealing to a {\it discrete Gauss-Bonnet theorem} (O. Knill, Elem. Math. 67, 1-17, 2012) which, as its continuous cousins, relates the sum/integral of the curvature to topological invariants. This leads to an exact geometric decomposition of the Heitmann-Radin energy into (i) a combinatorial bulk term, (ii) a combinatorial perimeter, (iii) a multiple of the Euler characteristic, and (iv) a natural topological energy contribution due to defects. An analogous exact geometric decomposition is also established for soft potentials such as the Lennard-Jones potential $V(r)=r^{-6}-2r^{-12}$, where two additional contributions arise, (v) elastic energy and (vi) energy due to non-bonded interactions.
The exact interaction energy of a many-electron system is determined by the electron pair density, which is not well-approximated in standard Kohn-Sham density functional models. Here we study the (complicated but well-defined) exact universal map from density to pair density. We survey how many common functionals, including the most basic version of the LDA (Dirac exchange with no correlation contribution), arise from particular approximations of this map. We develop an algorithm to compute the map numerically, and apply it to one-parameter families {a*rho(a*x)} of one-dimensional homogeneous and inhomogeneous single-particle densities. We observe that the pair density develops remarkable multiscale patterns which strongly depend on both the particle number and the "width" 1/a of the single-particle density. The simulation results are confirmed by rigorous asymptotic results in the limiting regimes a>>1 and a<<1. For one-dimensional homogeneous systems, we show that the whole spectrum of patterns is reproduced surprisingly well by a simple asymptotics-based ansatz which slowly smoothens out the "strictly correlated" a=0 pair density while slowly turning on the a=infty "exchange" terms as a increases. Our findings lend theoretical support to the celebrated semi-empirical idea [Becke93] to mix in a fractional amount of exchange, albeit not to assuming the mixing to be additive and taking the fraction to be a system independent constant.
Conventional X-ray methods use incoming plane waves and result in discrete diffraction patterns when scattered at crystals. Here we find, by a systematic method, incoming waveforms which exhibit discrete diffraction patterns when scattered at helical structures. As examples we present simulated diffraction patterns of carbon nanotubes and tobacco mosaic virus. The new incoming waveforms, which we call twisted waves due to their geometric shape, are found theoretically as closed-form solutions to Maxwell's equations. The theory of the ensuing diffraction patterns is developed in detail. A twisted analogue of the Von Laue condition is seen to hold, with the peak locations encoding the symmetry and the helix parameters, and the peak intensities indicating the electronic structure in the unit cell. If suitable twisted X-ray sources can in the future be realized experimentally, it appears from our mathematical results that they will provide a powerful tool for directly determining the detailed atomic structure of numerous biomolecules and nanostructures with helical symmetries. This would eliminate the need to crystallize those structures or their subunits.
In this paper, we study numerical discretizations to solve density functional models in the "strictly correlated electrons" (SCE) framework. Unlike previous studies our work is not restricted to radially symmetric densities. In the SCE framework, the exchange-correlation functional encodes the effects of the strong correlation regime by minimizing the pairwise Coulomb repulsion, resulting in an optimal transport problem. We give a mathematical derivation of the self-consistent Kohn-Sham-SCE equations, construct an efficient numerical discretization for this type of problem for N = 2 electrons, and apply it to the H2 molecule in its dissociating limit. Moreover, we prove that the SCE density functional model is correct for the H2 molecule in its dissociating limit.
We introduce and analyze symmetric infinite-body optimal transport (OT) problems with cost function of pair potential form. We show that for a natural class of such costs, the optimizer is given by the independent product measure all of whose factors are given by the one-body marginal. This is in striking contrast to standard finite-body OT problems, in which the optimizers are typically highly correlated, as well as to infinite-body OT problems with Gangbo-Swiech cost. Moreover, by adapting a construction from the study of exchangeable processes in probability theory, we prove that the corresponding $N$-body OT problem is well approximated by the infinite-body problem. To our class belongs the Coulomb cost which arises in many-electron quantum mechanics. The optimal cost of the Coulombic N-body OT problem as a function of the one-body marginal density is known in the physics and quantum chemistry literature under the name SCE functional, and arises naturally as the semiclassical limit of the celebrated Hohenberg-Kohn functional. Our results imply that in the inhomogeneous high-density limit (i.e. $N\to\infty$ with arbitrary fixed inhomogeneity profile $ρ/N$), the SCE functional converges to the mean field functional. We also present reformulations of the infinite-body and N-body OT problems as two-body OT problems with representability constraints and give a dual characterization of representable two-body measures which parallels an analogous result by Kummer on quantum representability of two-body density matrices.
We derive and analyze a hierarchy of approximations to the strongly correlated limit of the Hohenberg-Kohn functional. These "density representability approximations" are obtained by first noting that in the strongly correlated limit, N-representability of the pair density reduces to the requirement that the pair density must come from a symmetric N-point density. One then relaxes this requirement to the existence of a representing symmetric k-point density with k < N. The approximate energy can be computed by simulating a fictitious k-electron system. We investigate the approximations by deriving analytically exact results for a 2-site model problem, and by incorporating them into a self-consistent Kohn-Sham calculation for small atoms. We find that the low order representability conditions already capture the main part of the correlations.