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.Comment: To appear in J. Math. Phy

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 Schr\"odinger 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.Comment: 14 pages, 1 figur

Smoothing of Transport Plans with Fixed Marginals and Rigorous Semiclassical Limit of the Hohenberg–Kohn Functional

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 (Cotar etal. in Commun Pure Appl Math 66:548–599, 2013). The correct limit problem has been derived in the physics literature by Seidl (Phys Rev A 60 4387–4395, 1999) and Seidl, Gorigiorgi and Savin (Phys Rev A 75:042511 1-12, 2007); in these papers the lack of a rigorous proofwas pointed out.We also give amathematical 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

A Study Of A New Class Of Discrete Nonlinear Schroedinger Equations

A new class of 1D discrete nonlinear Schr${\ddot{\rm{o}}}$dinger Hamiltonians with tunable nonlinerities is introduced, which includes the integrable Ablowitz-Ladik system as a limit. A new subset of equations, which are derived from these Hamiltonians using a generalized definition of Poisson brackets, and collectively refered to as the N-AL equation, is studied. The symmetry properties of the equation are discussed. These equations are shown to possess propagating localized solutions, having the continuous translational symmetry of the one-soliton solution of the Ablowitz-Ladik nonlinear Schr${\ddot{\rm{o}}}$dinger equation. The N-AL systems are shown to be suitable to study the combined effect of the dynamical imbalance of nonlinearity and dispersion and the Peierls-Nabarro potential, arising from the lattice discreteness, on the propagating solitary wave like profiles. A perturbative analysis shows that the N-AL systems can have discrete breather solutions, due to the presence of saddle center bifurcations in phase portraits. The unstaggered localized states are shown to have positive effective mass. On the other hand, large width but small amplitude staggered localized states have negative effective mass. The collison dynamics of two colliding solitary wave profiles are studied numerically. Notwithstanding colliding solitary wave profiles are seen to exhibit nontrivial nonsolitonic interactions, certain universal features are observed in the collison dynamics. Future scopes of this work and possible applications of the N-AL systems are discussed.Comment: 17 pages, 15 figures, revtex4, xmgr, gn

Translationally invariant nonlinear Schrodinger lattices

Persistence of stationary and traveling single-humped localized solutions in the spatial discretizations of the nonlinear Schrodinger (NLS) equation is addressed. The discrete NLS equation with the most general cubic polynomial function is considered. Constraints on the nonlinear function are found from the condition that the second-order difference equation for stationary solutions can be reduced to the first-order difference map. The discrete NLS equation with such an exceptional nonlinear function is shown to have a conserved momentum but admits no standard Hamiltonian structure. It is proved that the reduction to the first-order difference map gives a sufficient condition for existence of translationally invariant single-humped stationary solutions and a necessary condition for existence of single-humped traveling solutions. Other constraints on the nonlinear function are found from the condition that the differential advance-delay equation for traveling solutions admits a reduction to an integrable normal form given by a third-order differential equation. This reduction also gives a necessary condition for existence of single-humped traveling solutions. The nonlinear function which admits both reductions defines a two-parameter family of discrete NLS equations which generalizes the integrable Ablowitz--Ladik lattice.Comment: 24 pages, 4 figure

Moving lattice kinks and pulses: an inverse method

We develop a general mapping from given kink or pulse shaped travelling-wave solutions including their velocity to the equations of motion on one-dimensional lattices which support these solutions. We apply this mapping - by definition an inverse method - to acoustic solitons in chains with nonlinear intersite interactions, to nonlinear Klein-Gordon chains, to reaction-diffusion equations and to discrete nonlinear Schr\"odinger systems. Potential functions can be found in at least a unique way provided the pulse shape is reflection symmetric and pulse and kink shapes are at least $C^2$ functions. For kinks we discuss the relation of our results to the problem of a Peierls-Nabarro potential and continuous symmetries. We then generalize our method to higher dimensional lattices for reaction-diffusion systems. We find that increasing also the number of components easily allows for moving solutions.Comment: 15 pages, 5 figure

Shape selection in non-Euclidean plates

We investigate isometric immersions of disks with constant negative curvature into $\mathbb{R}^3$, and the minimizers for the bending energy, i.e. the $L^2$ norm of the principal curvatures over the class of $W^{2,2}$ isometric immersions. We show the existence of smooth immersions of arbitrarily large geodesic balls in $\mathbb{H}^2$ into $\mathbb{R}^3$. In elucidating the connection between these immersions and the non-existence/singularity results of Hilbert and Amsler, we obtain a lower bound for the $L^\infty$ norm of the principal curvatures for such smooth isometric immersions. We also construct piecewise smooth isometric immersions that have a periodic profile, are globally $W^{2,2}$, and have a lower bending energy than their smooth counterparts. The number of periods in these configurations is set by the condition that the principal curvatures of the surface remain finite and grows approximately exponentially with the radius of the disc. We discuss the implications of our results on recent experiments on the mechanics of non-Euclidean plates

Setting and analysis of the multi-configuration time-dependent Hartree-Fock equations

In this paper we motivate, formulate and analyze the Multi-Configuration Time-Dependent Hartree-Fock (MCTDHF) equations for molecular systems under Coulomb interaction. They consist in approximating the N-particle Schrodinger wavefunction by a (time-dependent) linear combination of (time-dependent) Slater determinants. The equations of motion express as a system of ordinary differential equations for the expansion coefficients coupled to nonlinear Schrodinger-type equations for mono-electronic wavefunctions. The invertibility of the one-body density matrix (full-rank hypothesis) plays a crucial role in the analysis. Under the full-rank assumption a fiber bundle structure shows up and produces unitary equivalence between convenient representations of the equations. We discuss and establish existence and uniqueness of maximal solutions to the Cauchy problem in the energy space as long as the density matrix is not singular. A sufficient condition in terms of the energy of the initial data ensuring the global-in-time invertibility is provided (first result in this direction). Regularizing the density matrix breaks down energy conservation, however a global well-posedness for this system in L^2 is obtained with Strichartz estimates. Eventually solutions to this regularized system are shown to converge to the original one on the time interval when the density matrix is invertible.Comment: 48 pages, 1 figur

Periodic Travelling Waves in Dimer Granular Chains

We study bifurcations of periodic travelling waves in granular dimer chains from the anti-continuum limit, when the mass ratio between the light and heavy beads is zero. We show that every limiting periodic wave is uniquely continued with respect to the mass ratio parameter and the periodic waves with the wavelength larger than a certain critical value are spectrally stable. Numerical computations are developed to study how this solution family is continued to the limit of equal mass ratio between the beads, where periodic travelling waves of granular monomer chains exist

Derivation of a linearised elasticity model from singularly perturbed multiwell energy functionals

Linear elasticity can be rigorously derived from finite elasticity under the assumption of small loadings in terms of Gamma-convergence. This was first done in the case of one-well energies with super-quadratic growth and later generalised to different settings, in particular to the case of multi-well energies where the distance between the wells is very small (comparable to the size of the load). In this paper we study the case when the distance between the wells is independent of the size of the load. In this context linear elasticity can be derived by adding to the multi-well energy a singular higher order term which penalises jumps from one well to another. The size of the singular term has to satisfy certain scaling assumptions whose optimality is shown in most of the cases. Finally, the derivation of linear elasticty from a two-well discrete model is provided, showing that the role of the singular perturbation term is played in this setting by interactions beyond nearest neighbours