We study the Hartree-Fock equation and the Hartree-Fock energy functional universally used in many-electron problems. We prove that the set of all critical values of the Hartree-Fock energy functional less than a constant smaller than the first energy threshold is finite. Since the Hartree-Fock equation which is the corresponding Euler-Lagrange equation is a system of nonlinear eigenvalue problems, the spectral theory for linear operators is not applicable. The present result is obtained establishing the finiteness of the critical values associated with orbital energies less than a negative constant and combining the result with the Koopmans' well-known theorem. The main ingredients are the proof of convergence of the solutions and the analysis of the Fréchet second derivative of the functional at the limit point.
In this paper we study the problem of uniqueness of solutions to the Hartree and Hartree-Fock equations of atoms. We show, for example, that the Hartree-Fock ground state of a closed shell atom is unique provided the atomic number $Z$ is sufficiently large compared to the number $N$ of electrons. More specifically, a two-electron atom with atomic number $Z\geq 35$ has a unique Hartree-Fock ground state given by two orbitals with opposite spins and identical spatial wave functions. This statement is wrong for some $Z>1$, which exhibits a phase segregation.
In this note we establish the existence of ground states for atoms within several restricted Hartree-Fock theories. It is shown, for example, that there exists a ground state for closed shell atoms with $N$ electrons and nuclear charge $Z \geq N-1$. This has to be compared with the general Hartree-Fock theory where the existence of a minimizer is known for $Z>N-1$ only.
We study the Hartree-Fock model for pseudorelativistic atoms, that is, atoms where the kinetic energy of the electrons is given by the pseudorelativistic operator \sqrt{(pc)^2+(mc^2)^2}-mc^2. We prove the existence of a Hartree-Fock minimizer, and prove regularity away from the nucleus and pointwise exponential decay of the corresponding orbitals.
We prove the ionization conjecture within the Hartree-Fock theory of atoms. More precisely, we prove that, if the nuclear charge is allowed to tend to infinity, the maximal negative ionization charge and the ionization energy of atoms nevertheless remain bounded. Moreover, we show that in Hartree-Fock theory the radius of an atom (properly defined) is bounded independently of its nuclear charge.
We consider a molecule described by the Hartree-Fock model without the exchange term. We prove that nuclei of total charge $Z$ can bind at most $Z+C$ electrons, where $C$ is a constant independent of $Z$.
We prove within the Hartree-Fock theory of pseudo-relativistic atoms that the maximal negative ionization charge and the ionization energy of an atom remain bounded independently of the nuclear charge Z and the fine structure constant αas long as Zαis bounded.
We study the energy of relativistic electrons and positrons interacting via the second quantized Coulomb potential in the field of a nucleus of charge Z within the Hartree-Fock approximation. We show that the associated functional has a minimizer. In addition, all minimizers are purely electronic states, they are projections, and fulfill the no-pair Dirac-Fock equations.
We study the Wick symbol of a solution of the time dependent Hartree Fock equation, under weaker hypotheses than those needed for the Weyl symbol in the first paper with thesame title. With similar, we prove some kind of Ehrenfest theorem for observables that are not pseudo-differential operators.
We review recent results about the derivation and the analysis of two Hartree-Fock-type models for the polarization of vacuum. We pay particular attention to the variational construction of a self-consistent polarized vacuum, and to the physical agreement between our non-perturbative construction and the perturbative description provided by Quantum Electrodynamics.
We review some results of our paper arXiv:1602.05171v2 on the "nonlinear quasifree approximation" to the many-body Schrödinger dynamics of Bose gases. In that paper, we derive, with the help of this approximation, the time-dependent Hartree-Fock-Bogoliubov (HFB) equations, providing an approximate description of the dynamics of quantum fluctuations around a Bose-Einstein condensate and study properties of these equations.
The time-dependent Hartree-Fock equations are derived from the N-particle Schrödinger equation with mean-field scaling in the infinite particle limit, for initial data that are like Slater determinants. Only the case of bounded interaction potentials is treated in this work. We prove that, in the infnite particle limit, the first partial trace of the N-particle density operator approaches the solution of the time-dependent Hartree-Fock equations in the trace norm.
We study the ground state solutions of the Dirac-Fock model in the case of weak electronic repulsion, using bifurcation theory. They are solutions of a min-max problem. Then we investigate a max-min problem coming from the electron-positron field theory of Bach-Barbaroux-Helffer-Siedentop. We show that given a radially symmetric nuclear charge, the ground state of Dirac-Fock solves this max-min problem for certain numbers of electrons. But we also exhibit a situation in which the max-min level does not correspond to a solution of the Dirac-Fock equations together with its associated self-consi…
Hartree--Fock theory in quantum mechanics is reviewed, from the proposal of the Hartree--Fock approximation right after quantum mechanics was formulated to its applications in modern physics. This includes the description of traditional Hartree--Fock theory in quantum chemistry, its generalizations of various kinds, and its importance for predicting the presence of symmetry breaking, or the absence thereof.
We study the periodic Hartree-Fock model used for the description of electrons in a crystal. The existence of a minimizer was previously shown by Catto, Le Bris and Lions (Ann. Inst. H. Poincare Anal. Non Lineaire} 18 (2001), no.6, 687--760). We prove in this paper that any minimizer is necessarily a projector and that it solves a certain nonlinear equation, similarly to the atomic case. In particular we show that the Fermi level is either empty or totally filled.
We study the time evolution of the Weyl symbol of a solution of the time dependent Hartree Fock equation, assuming that for t=0, it has a Weyl symbol which is integrable in the phase space, such as all its derivatives. We prove that the solution has the same property for all t, and we give an asymptotic expansion, in L1 sense, of this Weyl symbol.
We study the dynamics of a Fermi gas with a Coulomb interaction potential, and show that, in a mean-field limiting regime, the dynamics is described by the Hartree-Fock equation. This extends previous work of Bardos et al. to the case of unbounded interaction potentials. We also express the mean-field limit as a "superhamiltonian" system, and state our main result in terms of a Heisenberg-picture dynamics of observables. This is a Egorov-type theorem.
Using the fractional moment method it is shown that, within the Hartree-Fock approximation for the Disordered Hubbard Hamiltonian, weakly interacting Fermions at positive temperature exhibit localization, suitably defined as exponential decay of eigenfunction correlators. Our result holds in any dimension in the regime of large disorder and at any disorder in the one dimensional case. As a consequence of our methods, we are able to show Hölder continuity of the integrated density of states with respect to energy, disorder and interaction using known techniques.
We review recent results concerning the evolution of fermionic systems. We are interested in the mean field regime, where particles experience many weak collisions. For fermions, the mean field regime is naturally linked with a semiclassical limit. Assuming some regularity of the interaction potential we show that the many body evolution of initial states close to Slater determinants exhibiting the appropriate semiclassical structure can be approximated by the Hartree-Fock equation. Our method provides precise bounds on the rate of the convergence.
We prove finite-time blowup for spherically symmetric and negative energy solutions of Hartree-Fock and Hartree-Fock-Bogoliubov type equations, which describe the evolution of attractive fermionic systems (e. g. white dwarfs). Our main results are twofold: First, we extend the recent blowup result of [Hainzl and Schlein, Comm. Math. Phys. \textbf{287} (2009), 705--714] to Hartree-Fock equations with infinite rank solutions and a general class of Newtonian type interactions. Second, we show the existence of finite-time blowup for spherically symmetric solutions of a Hartree-Fock-Bogoliubov mode…
We prove blow-up in finite time for radially symmetric solutions to the pseudo-relativistic Hartree-Fock equation with negative energy. The non-linear Hartree-Fock equation is commonly used in the physics literature to describe the dynamics of white dwarfs. We extend thereby recent results by Fröhlich and Lenzmann, who established in \cite{FL1,FL2} blow-up for solutions to the pseudo-relativistic Hartree equation. As key ingredient for handling the exchange term we use the conservation of the expectation of the square of the angular momentum operator.
For neutral and positively charged atoms and molecules, we prove the existence of infinitely many Hartree-Fock critical points below the first energy threshold (that is, the lowest energy of the same system with one electron removed). This is the equivalent, in Hartree-Fock theory, of the famous Zhislin-Sigalov theorem which states the existence of infinitely many eigenvalues below the bottom of the essential spectrum of the $N$-particle linear Schr{ö}dinger operator. Our result improves a theorem of Lions in 1987 who already constructed infinitely many Hartree-Fock critical points, but with m…
We study finite-time blow-up for pseudo-relativistic Hartree- and Hartree-Fock equations, which are model equations for the dynamical evolution of white dwarfs. In particular, we prove that radially symmetric initial configurations with negative energy lead to finite-time blow-up of solutions. Furthermore, we derive a mass concentration estimate for radial blow-up solutions. Both results are mathematically rigorous and are in accordance with Chandrasekhar's physical theory of white dwarfs, stating that stellar configurations beyond a certain limiting mass lead to ``gravitational collapse'' of …
We demonstrate that the reduced Hartree-Fock equation (REHF) with a small Anderson type background charge distribution has an unique stationary solution by explicitly computing a screening mass at positive temperature.
We generalize the Cramer's rule of linear algebra. We apply it to calculate the spectra of nucleus by applying Hill-Wheeler projection operator to Hartree-Fock wave function, and to derive Löwdin formula and Thouless theorem. We derive by an elementary method the infinitesimal or Löwdin projection operators and its integral representation to be useful for the projection of Slater determinant.
We will give a proof that the maximal excess charge for an atom described by a family of density-matrix-functionals, which includes Hartree-Fock and Müller theories, is bounded by an universal constant. We will use the new technique introduced by Frank et al (arXiv:1608.05625 [math-ph]).
We present a density matrix approach for computing global solutions of Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems. Equality of the upper- and lower-bound energies guarantees that the computed solution is the globally optimal solution of Hartree-Fock theory. For strongly correlated systems the SDP approach requires us to reassess the accuracy of the Hartree-Fock energies and densities from standard software packages for electronic structure theory. Calculations of the H$_{4}$ dimer and N$_{2}$ mol…
We prove the existence of solutions of the reduced Hartree-Fock equations at finite temperature for a periodic crystal with a small defect, and show total screening of the defect charge by the electrons. We also show the convergence of the damped self-consistent field iteration using Kerker preconditioning to remove charge sloshing. As a crucial step of the proof, we define and study the properties of the dielectric operator.
We prove decay with respect to some Lebesgue norms for a class of Schrödinger equations with non-local nonlinearities by showing new Morawetz inequalities and estimates. As a byproduct, we obtain large-data scattering in the energy space for the solutions to the systems of $N$ defocusing Schrödinger-Choquard equations with mass-energy intercritical nonlinearities in any space dimension and of defocusing Hartree-Fock equations, for any dimension $d\geq3$.
We show that there is an one-to-one correspondence between solutions to the Poisson-Landscape equations and the reduced Hartree-Fock equations in the semi-classical limit at low temperature. Moreover, we prove that the difference between the two corresponding solutions is small by providing explicit estimates.
We study the dynamics of the thermal momentum distribution function for an interacting, homogenous Fermi gas on $\Z^3$ in the presence of an external weak static random potential, where the pair interactions between the fermions are modeled in dynamical Hartree-Fock theory. We determine the Boltzmann limits associated to different scaling regimes defined by the size of the random potential, and the strength of the fermion interactions.
We prove analytic-type estimates in weighted Sobolev spaces on the eigenfunctions of a class of elliptic and nonlinear eigenvalue problems with singular potentials, which includes the Hartree-Fock equations. Going beyond classical results on the analyticity of the wavefunctions away from the nuclei, we prove weighted estimates locally at each singular point, with precise control of the derivatives of all orders. Our estimates have far-reaching consequences for the approximation of the eigenfunctions of the problems considered, and they can be used to prove a priori estimates on the numerical s…
We prove the existence of minimizers for Hartree-Fock-Bogoliubov (HFB) energy functionals with attractive two-body interactions given by Newtonian gravity. This class of HFB functionals serves as model problem for self-gravitating relativistic Fermi systems, which are found in neutron stars and white dwarfs. Furthermore, we derive some fundamental properties of HFB minimizers such as a decay estimate for the minimizing density. A decisive feature of the HFB model in gravitational physics is its failure of weak lower semicontinuity. This fact essentially complicates the analysis compared to the…
We consider the gravitational collapse for neutron stars in the Hartree-Fock-Bogoliubov theory. We prove that when the number particle becomes large and the gravitational constant is small such that the attractive interaction strength approaches the Chandrasekhar limit mass slowly, the minimizers develop a universal blow-up profile. It is given by the Lane-Emden solution.
We find the general solution to the time-dependent Hartree-Fock problem for the Gross-Neveu models, with both discrete (GN2) and continuous (NJL2) chiral symmetry. We find new multi-baryon, multi-breather and twisted breather solutions, and show that all GN2 baryons and breathers are composed of constituent twisted kinks of the NJL2 model.
The domain of validity of the higher-order Schrodinger equations is analyzed for harmonic-oscillator and Coulomb potentials as typical examples. Then the Cauchy theory for higher-order Hartree-Fock equations with bounded and Coulomb potentials is developed. Finally, the existence of associated ground states for the odd-order equations is proved. This renders these quantum equations relevant for physics.
We study the Hartree-Fock approximation of graphene in infinite volume, with instantaneous Coulomb interactions. First we construct its translation-invariant ground state and we recover the well-known fact that, due to the exchange term, the effective Fermi velocity is logarithmically divergent at zero momentum. In a second step we prove the existence of a ground state in the presence of local defects and we discuss some properties of the linear response to an external electric field. All our results are non perturbative.
