Relativistic atomic level calculations with nuclei carrying additional fractional charges

One-electron energy levels and wavelengths have been calculated for Na-like ions whose nuclei carry quarks with additional charges ±e/3, ±2e/3. The calculations are based on relativistic self-consistent field procedures. The deviations from experimental values exhibit regularities which allow an extrapolation for the wavelengths of 3s - 3p, 3s - 4p, 3p - 3d, and 3p - 4s transitions for the nuclear charge Z = 11± 1/3, ±2/3. A number of transitions are found in the region of visible light which could be used in an optical search for quark atoms.

Elastic nuclear scattering at intermediate and relativistic energies

The classical scattering cross section of two colliding nuclei at intermediate and relativistic energies is reevaluated. The influence of retardation and magnetic field effects is taken into account. Corrections due to electron screening as well as due to attractive nuclear forces are discussed. This paper represents an addendum to [l].

Solution of the Hartree-Fock-Slater equations for diatomic molecules by the finite-element method

We present the finite-element method in its application to solving quantum-mechanical problems for diatomic molecules. Results for Hartree-Fock calculations of H_2 and Hartree-Fock-Slater calculations for molecules like N_2 and CO are presented. The accuracy achieved with fewer than 5000 grid points for the total energies of these systems is 10^-8 a.u., which is about two orders of magnitude better than the accuracy of any other available method.

Relativistic molecular calculations of superheavy molecules

Relativistic molecular calculations within the Dirac-Slater scheme have been used in a study of the electronic structure of 6d-metal superheavy hexafluorides. The theoretical results are compared with calculations and measurements of the homolog 4d- and 5d-metal hexafluorides. Large spin-orbit splitting dominates the electronic structure and even has the same order of magnitude as the crystal-field splitting for the valence electrons for the superheavy molecules. Ionization energies have been calculated using a transition state procedure.

Self-consistent relativistic molecular calculations of superheavy molecules: (_110 X)F_6

Using new relativistic molecular calculations within the Dirac-Slater scheme it is now feasible to study theoretically molecules containing superheavy elements. This opens a new era for the prediction of the physics and chemistry of superheavy elements. As an example we present the results for (_110 X) F_6, where it is shown that relativistic effects are nearly of the same order of magnitude as the crystal-field splitting.

Computation of relativistic symmetry orbitals for finite double point groups

A program is presented for the construction of relativistic symmetry-adapted molecular basis functions. It is applicable to 36 finite double point groups. The algorithm, based on the projection operator method, automatically generates linearly independent basis sets. Time reversal invariance is included in the program, leading to additional selection rules in the non-relativistic limit.

Test for basis-set errors in relativistic Dirac-Fock-Slater calculations with a numerical AO-DFS-basis

A fully relativistic four-component Dirac-Fock-Slater program for diatomics, with numerically given AO's as basis functions is presented. We discuss the problem of the errors due to the finite basis-set, and due to the influence of the negative energy solutions of the Dirac Hamiltonian. The negative continuum contributions are found to be very small.

Non-relativistic and relativistic molecular calculations for the chalcogen hexafluorides: SF_6, SeF_6, TeF_6, PoF_6

Non-relativistic Hartree-Fock-Slater and relativistic Dirac-Slater self-consistent orbital models are applied for the analysis of the electronic structure of the chalcogen hexafluorides: SF_6, SeF_6, TeF_6 and PoF_6. The molecular eigenfunctions and eigenvalues are generated using the discrete variational method (DVM) with numerical basis functions. The results obtained for SF_6 are compared with other ab initio calculations. Information about relativistic level shifts and spin-orbit splitting has been obtained by comparison between the non-relativistic and relativistic results.

Femtosecond time-resolved wave packet motion in molecular multiphoton ionization and fragmentation

The dynamics of molecular multiphoton ionization and fragmentation of a diatomic molecule (Na_2) have been studied in molecular beam experiments. Femtosecond laser pulses from an amplified colliding-pulse mode-locked (CPM) ring dye laser are employed to induce and probe the molecular transitions. The final continuum states are analyzed by photoelectron spectroscopy, by ion mass spectrometry and by measuring the kinetic energy of the formed ionic fragments. Pump-probe spectra employing 70-fs laser pulses have been measured to study the time dependence of molecular multiphoton ionization and fragmentation. The oscillatory structure of the transient spectra showing the dynamics on the femtosecond time scale can best be understood in terms of the motion of wave packets in bound molecular potentials. The transient Na_2^+ ionization and the transient Na^+ fragmentation spectra show that contributions from direct photoionization of a singly excited electronic state and from excitation and autoionization of a bound doubly excited molecular state determine the time evolution of molecular multiphoton ionization.

Femtosecond pump-probe study of the spreading and recurrence of a vibrational wave packet in Na_2

The motion of a vibrational wave packet in the bound A(^1 \summe^+_u) electronic state of the sodium dimer is detected in a femtosecond pump/probe molecular beam experiment. For short times harmonic motion is seen in the total ion yield of Na^+_2 as a function of delay time between the two laser pulses. The spreading of the wave packet results in the loss of the periodic variation of the ion signal. For longer delay times (47 ps) the wave packet regains its initial form which is reflected in the revival structure of the Na^+_2 signal. Time-dependent quantum calculations reproduce the measured effects.

An introduction to ordinary differential equations by computer algebra-systems

We report on an elementary course in ordinary differential equations (odes) for students in engineering sciences. The course is also intended to become a self-study package for odes and is is based on several interactive computer lessons using REDUCE and MATHEMATICA . The aim of the course is not to do Computer Algebra (CA) by example or to use it for doing classroom examples. The aim ist to teach and to learn mathematics by using CA-systems.

Analytical Study of Light Propagation in Highly Nonlinear Media

The present dissertation is devoted to the construction of exact and approximate analytical solutions of the problem of light propagation in highly nonlinear media. It is demonstrated that for many experimental conditions, the problem can be studied under the geometrical optics approximation with a sufficient accuracy. Based on the renormalization group symmetry analysis, exact analytical solutions of the eikonal equations with a higher order refractive index are constructed. A new analytical approach to the construction of approximate solutions is suggested. Based on it, approximate solutions for various boundary conditions, nonlinear refractive indices and dimensions are constructed. Exact analytical expressions for the nonlinear self-focusing positions are deduced. On the basis of the obtained solutions a general rule for the single filament intensity is derived; it is demonstrated that the scaling law (the functional dependence of the self-focusing position on the peak beam intensity) is defined by a form of the nonlinear refractive index but not the beam shape at the boundary. Comparisons of the obtained solutions with results of experiments and numerical simulations are discussed.

Relativistic LCAO with Minimax Principle and New Balanced Basis Sets

Relativistic density functional theory is widely applied in molecular calculations with heavy atoms, where relativistic and correlation effects are on the same footing. Variational stability of the Dirac Hamiltonian is a very important field of research from the beginning of relativistic molecular calculations on, among efforts for accuracy, efficiency, and density functional formulation, etc. Approximations of one- or two-component methods and searching for suitable basis sets are two major means for good projection power against the negative continuum. The minimax two-component spinor linear combination of atomic orbitals (LCAO) is applied in the present work for both light and super-heavy one-electron systems, providing good approximations in the whole energy spectrum, being close to the benchmark minimax finite element method (FEM) values and without spurious and contaminated states, in contrast to the presence of these artifacts in the traditional four-component spinor LCAO. The variational stability assures that minimax LCAO is bounded from below. New balanced basis sets, kinetic and potential defect balanced (TVDB), following the minimax idea, are applied with the Dirac Hamiltonian. Its performance in the same super-heavy one-electron quasi-molecules shows also very good projection capability against variational collapse, as the minimax LCAO is taken as the best projection to compare with. The TVDB method has twice as many basis coefficients as four-component spinor LCAO, which becomes now linear and overcomes the disadvantage of great time-consumption in the minimax method. The calculation with both the TVDB method and the traditional LCAO method for the dimers with elements in group 11 of the periodic table investigates their difference. New bigger basis sets are constructed than in previous research, achieving high accuracy within the functionals involved. Their difference in total energy is much smaller than the basis incompleteness error, showing that the traditional four-spinor LCAO keeps enough projection power from the numerical atomic orbitals and is suitable in research on relativistic quantum chemistry. In scattering investigations for the same comparison purpose, the failure of the traditional LCAO method of providing a stable spectrum with increasing size of basis sets is contrasted to the TVDB method, which contains no spurious states already without pre-orthogonalization of basis sets. Keeping the same conditions including the accuracy of matrix elements shows that the variational instability prevails over the linear dependence of the basis sets. The success of the TVDB method manifests its capability not only in relativistic quantum chemistry but also for scattering and under the influence of strong external electronic and magnetic fields. The good accuracy in total energy with large basis sets and the good projection property encourage wider research on different molecules, with better functionals, and on small effects.

On Solutions of Holonomic Divided-Difference Equations on Non-Uniform Lattices

The main aim of this paper is the development of suitable bases (replacing the power basis x^n (n\in\IN_\le 0) which enable the direct series representation of orthogonal polynomial systems on non-uniform lattices (quadratic lattices of a discrete or a q-discrete variable). We present two bases of this type, the first of which allows to write solutions of arbitrary divided-difference equations in terms of series representations extending results given in [16] for the q-case. Furthermore it enables the representation of the Stieltjes function which can be used to prove the equivalence between the Pearson equation for a given linear functional and the Riccati equation for the formal Stieltjes function. If the Askey-Wilson polynomials are written in terms of this basis, however, the coefficients turn out to be not q-hypergeometric. Therefore, we present a second basis, which shares several relevant properties with the first one. This basis enables to generate the defining representation of the Askey-Wilson polynomials directly from their divided-difference equation. For this purpose the divided-difference equation must be rewritten in terms of suitable divided-difference operators developed in [5], see also [6].

Electron-Nuclear Correlation in Laser-Driven Diatomic Molecules

The interaction of short intense laser pulses with atoms/molecules produces a multitude of highly nonlinear processes requiring a non-perturbative treatment. Detailed study of these highly nonlinear processes by numerically solving the time-dependent Schrodinger equation becomes a daunting task when the number of degrees of freedom is large. Also the coupling between the electronic and nuclear degrees of freedom further aggravates the computational problems. In the present work we show that the time-dependent Hartree (TDH) approximation, which neglects the correlation effects, gives unreliable description of the system dynamics both in the absence and presence of an external field. A theoretical framework is required that treats the electrons and nuclei on equal footing and fully quantum mechanically. To address this issue we discuss two approaches, namely the multicomponent density functional theory (MCDFT) and the multiconfiguration time-dependent Hartree (MCTDH) method, that go beyond the TDH approximation and describe the correlated electron-nuclear dynamics accurately. In the MCDFT framework, where the time-dependent electronic and nuclear densities are the basic variables, we discuss an algorithm to calculate the exact Kohn-Sham (KS) potentials for small model systems. By simulating the photodissociation process in a model hydrogen molecular ion, we show that the exact KS potentials contain all the many-body effects and give an insight into the system dynamics. In the MCTDH approach, the wave function is expanded as a sum of products of single-particle functions (SPFs). The MCTDH method is able to describe the electron-nuclear correlation effects as the SPFs and the expansion coefficients evolve in time and give an accurate description of the system dynamics. We show that the MCTDH method is suitable to study a variety of processes such as the fragmentation of molecules, high-order harmonic generation, the two-center interference effect, and the lochfrass effect. We discuss these phenomena in a model hydrogen molecular ion and a model hydrogen molecule. Inclusion of absorbing boundaries in the mean-field approximation and its consequences are discussed using the model hydrogen molecular ion. To this end, two types of calculations are considered: (i) a variational approach with a complex absorbing potential included in the full many-particle Hamiltonian and (ii) an approach in the spirit of time-dependent density functional theory (TDDFT), including complex absorbing potentials in the single-particle equations. It is elucidated that for small grids the TDDFT approach is superior to the variational approach.