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Gero Friesecke

Publications and source records attributed to Gero Friesecke.

48 records · Page 3Linked to original sources
arXiv2012

Cnoidal Waves on Fermi-Pasta-Ulam Lattices

We study a chain of infinitely many particles coupled by nonlinear springs, obeying the equations of motion [\ddot{q}_n = V'(q_{n+1}-q_n) - V'(q_n-q_{n-1})] with generic nearest-neighbour potential $V$. We show that this chain carries exact spatially periodic travelling waves whose profile is asymptotic, in a small-amlitude long-wave regime, to the KdV cnoidal waves. The discrete waves have three interesting features: (1) being exact travelling waves they keep their shape for infinite time, rather than just up to a timescale of order wavelength$^{-3}$ suggested by formal asymptotic analysis, (2) unlike solitary waves they carry a nonzero amount of energy per particle, (3) analogous behaviour of their KdV continuum counterparts suggests long-time stability properties under nonlinear interaction with each other. Connections with the Fermi-Pasta-Ulam recurrence phenomena are indicated. Proofs involve an adaptation of the renormalization approach of Friesecke and Pego (1999) to a periodic setting and the spectral theory of the periodic Schrödinger operator with KdV cnoidal wave potential.

math-ph↗
arXiv2011

Density functional theory and optimal transportation with Coulomb cost

We present here novel insight into exchange-correlation functionals in density functional theory, based on the viewpoint of optimal transport. We show that in the case of two electrons and in the semiclassical limit, the exact exchange-correlation functional reduces to a very interesting functional of novel form, which depends on an optimal transport map $T$ associated with a given density $ρ$. Since the above limit is strongly correlated, the limit functional yields insight into electron correlations. We prove the existence and uniqueness of such an optimal map for any number of electrons and each $ρ$, and determine the map explicitly in the case when $ρ$ is radially symmetric.

math.AP↗
arXiv2010

Efficient Algorithm for Asymptotics-Based Configuration-Interaction Methods and Electronic Structure of Transition Metal Atoms

Asymptotics-based configuration-interaction (CI) methods [G. Friesecke and B. D. Goddard, Multiscale Model. Simul. 7, 1876 (2009)] are a class of CI methods for atoms which reproduce, at fixed finite subspace dimension, the exact Schrödinger eigenstates in the limit of fixed electron number and large nuclear charge. Here we develop, implement, and apply to 3d transition metal atoms an efficient and accurate algorithm for asymptotics-based CI. Efficiency gains come from exact (symbolic) decomposition of the CI space into irreducible symmetry subspaces at essentially linear computational cost in the number of radial subshells with fixed angular momentum, use of reduced density matrices in order to avoid having to store wavefunctions, and use of Slater-type orbitals (STO's). The required Coulomb integrals for STO's are evaluated in closed form, with the help of Hankel matrices, Fourier analysis, and residue calculus. Applications to 3d transition metal atoms are in good agreement with experimental data. In particular we reproduce the anomalous magnetic moment and orbital filling of Chromium in the otherwise regular series Ca, Sc, Ti, V, Cr.

quant-ph↗
arXiv2010

Semiclassical limit of quantum dynamics with rough potentials and well posedness of transport equations with measure initial data

In this paper we study the semiclassical limit of the Schrödinger equation. Under mild regularity assumptions on the potential $U$ which include Born-Oppenheimer potential energy surfaces in molecular dynamics, we establish asymptotic validity of classical dynamics globally in space and time for "almost all" initial data, with respect to an appropriate reference measure on the space of initial data. In order to achieve this goal we prove existence, uniqueness and stability results for the flow in the space of measures induced by the continuity equation.

math.AP↗
arXiv2009

Minimizing atomic configurations of short range pair potentials in two dimensions: crystallization in the Wulff shape

We investigate ground state configurations of atomic systems in two dimensions interacting via short range pair potentials. As the number of particles tends to infinity, we show that low-energy configurations converge to a macroscopic cluster of finite surface area and constant density, the latter being given by the density of atoms per unit volume in the triangular lattice. In the special case of the Heitmann-Radin sticky disc potential and exact ground states, we show that the macroscopic cluster has a (unique) Wulff shape. This is done by showing that the atomistic energy, after subtracting off a bulk part and re-scaling, Gamma-converges to a macroscopic anisotropic surface energy.

math.AP↗
arXiv2009

Minimum energy configurations of classical charges: Large N asymptotics

We study minimum energy configurations of $N$ particles in $\R^3$ of charge -1 (`electrons') in the potential of $M$ particles of charges $Z_α>0$ (`atomic nuclei'). In a suitable large-N limit, we determine the asymptotic electron distribution explicitly, showing in particular that the number of electrons surrounding each nucleus is asymptotic to the nuclear charge ("screening"). The proof proceeds by establishing, via Gamma-convergence, a coarse-grained variational principle for the limit distribution, which can be solved explicitly.

math.CA↗
arXiv2009

Mean field approximation in conformation dynamics

We propose a new approach to the transfer operator based analysis of the conformation dynamics of molecules. It is based on a statistical independence ansatz for the eigenfunctions of the operator related to a partitioning into subsystems. Numerical tests performed on small systems show excellent qualitative agreement between mean field and exact model, at greatly reduced computational cost.

math.NA↗
arXiv2009

On the Ehrenfest theorem of quantum mechanics

We give a mathematically rigorous derivation of Ehrenfest's equations for the evolution of position and momentum expectation values, under general and natural assumptions which include atomic and molecular Hamiltonians with Coulomb interactions.

math-ph↗
arXiv2009

Explicit large nuclear charge limit of electronic ground states for Li, Be, B, C, N, O, F, Ne and basic aspects of the periodic table

This paper is concerned with the Schrödinger equation for atoms and ions with N=1 to 10 electrons. In the asymptotic limit of large nuclear charge $Z$, we determine explicitly the low-lying energy levels and eigenstates. The asymptotic energies and wavefunctions are in good quantitative agreement with experimental data for positive ions, and in excellent qualitative agreement even for neutral atoms ($Z=N$). In particular, the predicted ground state spin and angular momentum quantum numbers ($^1S$ for He, Be, Ne, $^2S$ for H and Li, $^4S$ for N, $^2P$ for B and F, and $^3P$ for C and O) agree with experiment in every case. The asymptotic Schrödinger ground states agree, up to small corrections, with the semi-empirical hydrogen orbital configurations developed by Bohr, Hund and Slater to explain the periodic table. In rare cases where our results deviate from this picture, such as the ordering of the lowest ${}^1D^o$ and ${}^3S^o$ states of the Carbon isoelectronic sequence, experiment confirms our, not Hund's, predictions.

math-ph↗
arXiv2009

Asymptotics-based CI models for atoms: properties, exact solution of a minimal model for Li to Ne, and application to atomic spectra

Configuration-Interaction (CI) models are approximations to the electronic Schrödinger equation which are widely used for numerical electronic structure calculations in quantum chemistry. Based on our recent closed-form asymptotic results for the full atomic Schrödinger equation in the limit of fixed electron number and large nuclear charge, we introduce a class of CI models for atoms which reproduce, at fixed finite model dimension, the correct Schrödinger eigenvalues and eigenstates in this limit. We solve exactly the ensuing minimal model for the second period atoms, Li to Ne. The energy levels and eigenstates are in remarkably good agreement with experimental data (comparable to that of much larger scale numerical simulations in the literature), and facilitate a mathematical understanding of various spectral, chemical and physical properties of small atoms.

math-ph↗