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 semiempirical 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 predictions and not Hund's

Radio emission of sea surface at centimeter wavelengths and is fluctuations

The eigen thermal radio emission of the sea was examined as well as the agitated surface of the sea when the reflection (scattering) is similar in nature to diffused scattering. The contribution of this emission to the total emission of the sea is practically constant in time, and the time fluctuations of the radio emissions of the sea are basically determined only by a change in the eigen emission of the sea, connected with the agitation

Bound States at Threshold resulting from Coulomb Repulsion

The eigenvalue absorption for a many-particle Hamiltonian depending on a parameter is analyzed in the framework of non-relativistic quantum mechanics. The long-range part of pair potentials is assumed to be pure Coulomb and no restriction on the particle statistics is imposed. It is proved that if the lowest dissociation threshold corresponds to the decay into two likewise non-zero charged clusters then the bound state, which approaches the threshold, does not spread and eventually becomes the bound state at threshold. The obtained results have applications in atomic and nuclear physics. In particular, we prove that atomic ion with atomic critical charge $Z_{cr}$ and $N_e$ electrons has a bound state at threshold given that $Z_{cr} \in (N_e -2, N_e -1)$, whereby the electrons are treated as fermions and the mass of the nucleus is finite.Comment: This is a combined and updated version of the manuscripts arXiv:math-ph/0611075v2 and arXiv:math-ph/0610058v

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

Heat kernel estimates and spectral properties of a pseudorelativistic operator with magnetic field

Based on the Mehler heat kernel of the Schroedinger operator for a free electron in a constant magnetic field an estimate for the kernel of E_A is derived, where E_A represents the kinetic energy of a Dirac electron within the pseudorelativistic no-pair Brown-Ravenhall model. This estimate is used to provide the bottom of the essential spectrum for the two-particle Brown-Ravenhall operator, describing the motion of the electrons in a central Coulomb field and a constant magnetic field, if the central charge is restricted to Z below or equal 86

Rigorous conditions for the existence of bound states at the threshold in the two-particle case

In the framework of non-relativistic quantum mechanics and with the help of the Greens functions formalism we study the behavior of weakly bound states as they approach the continuum threshold. Through estimating the Green's function for positive potentials we derive rigorously the upper bound on the wave function, which helps to control its falloff. In particular, we prove that for potentials whose repulsive part decays slower than $1/r^{2}$ the bound states approaching the threshold do not spread and eventually become bound states at the threshold. This means that such systems never reach supersizes, which would extend far beyond the effective range of attraction. The method presented here is applicable in the many--body case

Zero Energy Bound States in Many--Particle Systems

It is proved that the eigenvalues in the N--particle system are absorbed at zero energy threshold, if none of the subsystems has a bound state with $E \leq 0$ and none of the particle pairs has a zero energy resonance. The pair potentials are allowed to take both signs

On the Quantum Theory of Molecules

Transition state theory was introduced in the 1930s to account for chemical reactions. Central to this theory is the idea of a potential energy surface (PES). It was assumed that such a surface could be constructed using eigensolutions of the Schr\"{o}dinger equation for the molecular (Coulomb) Hamiltonian but at that time such calculations were not possible. Nowadays quantum mechanical ab-initio electronic structure calculations are routine and from their results PESs can be constructed which are believed to approximate those assumed derivable from the eigensolutions. It is argued here that this belief is unfounded. It is suggested that the potential energy surface construction is more appropriately regarded as a legitimate and effective modification of quantum mechanics for chemical purpose

Binding of Polarons and Atoms at Threshold

If the polaron coupling constant $\alpha$ is large enough, bipolarons or multi-polarons will form. When passing through the critical $\alpha_c$ from above, does the radius of the system simply get arbitrarily large or does it reach a maximum and then explodes? We prove that it is always the latter. We also prove the analogous statement for the Pekar-Tomasevich (PT) approximation to the energy, in which case there is a solution to the PT equation at $\alpha_c$. Similarly, we show that the same phenomenon occurs for atoms, e.g., helium, at the critical value of the nuclear charge. Our proofs rely only on energy estimates, not on a detailed analysis of the Schr\"odinger equation, and are very general. They use the fact that the Coulomb repulsion decays like $1/r$, while `uncertainty principle' localization energies decay more rapidly, as $1/r^2$.Comment: 19 page

A mathematical and computational review of Hartree-Fock SCF methods in Quantum Chemistry

We present here a review of the fundamental topics of Hartree-Fock theory in Quantum Chemistry. From the molecular Hamiltonian, using and discussing the Born-Oppenheimer approximation, we arrive to the Hartree and Hartree-Fock equations for the electronic problem. Special emphasis is placed in the most relevant mathematical aspects of the theoretical derivation of the final equations, as well as in the results regarding the existence and uniqueness of their solutions. All Hartree-Fock versions with different spin restrictions are systematically extracted from the general case, thus providing a unifying framework. Then, the discretization of the one-electron orbitals space is reviewed and the Roothaan-Hall formalism introduced. This leads to a exposition of the basic underlying concepts related to the construction and selection of Gaussian basis sets, focusing in algorithmic efficiency issues. Finally, we close the review with a section in which the most relevant modern developments (specially those related to the design of linear-scaling methods) are commented and linked to the issues discussed. The whole work is intentionally introductory and rather self-contained, so that it may be useful for non experts that aim to use quantum chemical methods in interdisciplinary applications. Moreover, much material that is found scattered in the literature has been put together here to facilitate comprehension and to serve as a handy reference.Comment: 64 pages, 3 figures, tMPH2e.cls style file, doublesp, mathbbol and subeqn package