The nonrelativistic limit of Dirac-Fock codes: the role of Brillouin configurations

We solve a long standing problem with relativistic calculations done with the widely used Multi-Configuration Dirac-Fock Method (MCDF). We show, using Relativistic Many-Body Perturbation Theory (RMBPT), how even for relatively high-$Z$, relaxation or correlation causes the non-relativistic limit of states of different total angular momentum but identical orbital angular momentum to have different energies. We show that only large scale calculations that include all single excitations, even those obeying the Brillouin's theorem have the correct limit. We reproduce very accurately recent high-precision measurements in F-like Ar, and turn then into precise test of QED. We obtain the correct non-relativistic limit not only for fine structure but also for level energies and show that RMBPT calculations are not immune to this problem.Comment: AUgust 9th, 2004 Second version Nov. 18th, 200

Exchange interaction and correlations radically change behaviour of a quantum particle in a classically forbidden region

Exchange interaction strongly influences the long-range behaviour of localised electron orbitals and quantum tunneling amplitudes. It violates the oscillation theorem (creates extra nodes) and produces a power-law decay instead of the usual exponential decrease at large distances. For inner orbitals inside molecules decay is $r^{-2}$, for macroscopic systems $\cos{(k_f r)} r^{-\nu}$, where $k_f$ is the Fermi momentum and $\nu=3$ for 1D, $\nu=$3.5 for 2D and $\nu=$4 for 3D crystal. Correlation corrections do not change these conclusions. Slow decay increases the exchange interaction between localized spins and the under-barrier tunneling amplitude. The under-barrier transmission coefficients in solids (e.g. for point contacts) become temperature-dependent

Exploring Biorthonormal Transformations of Pair-Correlation Functions in Atomic Structure Variational Calculations

Multiconfiguration expansions frequently target valence correlation and correlation between valence electrons and the outermost core electrons. Correlation within the core is often neglected. A large orbital basis is needed to saturate both the valence and core-valence correlation effects. This in turn leads to huge numbers of CSFs, many of which are unimportant. To avoid the problems inherent to the use of a single common orthonormal orbital basis for all correlation effects in the MCHF method, we propose to optimize independent MCHF pair-correlation functions (PCFs), bringing their own orthonormal one-electron basis. Each PCF is generated by allowing single- and double- excitations from a multireference (MR) function. This computational scheme has the advantage of using targeted and optimally localized orbital sets for each PCF. These pair-correlation functions are coupled together and with each component of the MR space through a low dimension generalized eigenvalue problem. Nonorthogonal orbital sets being involved, the interaction and overlap matrices are built using biorthonormal transformation of the coupled basis sets followed by a counter-transformation of the PCF expansions. Applied to the ground state of beryllium, the new method gives total energies that are lower than the ones from traditional CAS-MCHF calculations using large orbital active sets. It is fair to say that we now have the possibility to account for, in a balanced way, correlation deep down in the atomic core in variational calculations

On the AC spectrum of one-dimensional random Schroedinger operators with matrix-valued potentials

We consider discrete one-dimensional random Schroedinger operators with decaying matrix-valued, independent potentials. We show that if the l^2-norm of this potential has finite expectation value with respect to the product measure then almost surely the Schroedinger operator has an interval of purely absolutely continuous (ac) spectrum. We apply this result to Schroedinger operators on a strip. This work provides a new proof and generalizes a result obtained by Delyon, Simon, and Souillard.Comment: (1 figure

Symmetry Breaking of Relativistic Multiconfiguration Methods in the Nonrelativistic Limit

The multiconfiguration Dirac-Fock method allows to calculate the state of relativistic electrons in atoms or molecules. This method has been known for a long time to provide certain wrong predictions in the nonrelativistic limit. We study in full mathematical details the nonlinear model obtained in the nonrelativistic limit for Be-like atoms. We show that the method with sp+pd configurations in the J=1 sector leads to a symmetry breaking phenomenon in the sense that the ground state is never an eigenvector of L^2 or S^2. We thereby complement and clarify some previous studies.Comment: Final version, to appear in Nonlinearity. Nonlinearity (2010) in pres

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

A count in the dark

The Census of Marine Life has succeeded in raising awareness about marine biodiversity, and contributed much to our understanding of what lives where. But the project has fallen short of its goal to estimate species abundance

Relativistic transition wavelenghts and probabilities for spectral lines of Ne II

Transition wavelengths and probabilities for several 2p4 3p - 2p4 3s and 2p4 3d - 2p4 3p lines in fuorine-like neon ion (NeII) have been calculated within the multiconfiguration Dirac-Fock (MCDF) method with quantum electrodynamics (QED) corrections. The results are compared with all existing experimental and theoretical data

Relativistic total cross section and angular distribution for Rayleigh scattering by atomic hydrogen

We study the total cross section and angular distribution in Rayleigh scattering by hydrogen atom in the ground state, within the framework of Dirac relativistic equation and second-order perturbation theory. The relativistic states used for the calculations are obtained by making use of the finite basis set method and expressed in terms of B-splines and B-polynomials. We pay particular attention to the effects that arise from higher (non-dipole) terms in the expansion of the electron-photon interaction. It is shown that the angular distribution of scattered photons, while it is symmetric with respect to the scattering angle $\theta$=90$^\circ$ within the electric dipole approximation, becomes asymmetric when higher multipoles are taken into account. The analytical expression of the angular distribution is parametrized in terms of Legendre polynomials. Detailed calculations are performed for photons in the energy range 0.5 to 10 keV. When possible, results are compared with previous calculations.Comment: 8 pages, 5 figure