An attempt on the calculation of relativistic potential energy curves: noble gas difluorides

Total energy SCF calculations were performed for noble gas difluorides in a relativistic procedure and compared with analogous non-relativistic calculations. The discrete variational method with numerical basis functions was used. Rather smooth potential energy curves could be obtained. The theoretical Kr - F and Xe - F bond distances were calculated to be 3.5 a.u. and 3.6 a.u. which should be compared with the experimental values of 3.54 a.u. and 3.7 a.u. Although the dissociation energies are off by a factor of about five it was found that ArF_2 may be a stable molecule. Theoretical ionization energies for the outer levels reproduce the experimental values for KrF_2 and XeF_2 to within 2 eV.

Interpretation of quasimolecular L X-rays in heavy-ion collisions

Using a relativistic selfconsistent correlation diagram a first interpretation of the shape and position of L MO X-rays is given within a quasi-adiabatic model.

Interpretation of noncharacteristic M X-rays in heavy colliding systems by selfconsistent relativistic molecular calculations

The result of the first calculation of a self-consistent relativistic many electron correlation diagram ever done (for the system Au - I) leads to a good agreement of the spectral shape and position of the observed noncharacteristic X-rays within the quasi adiabatic model.

An ab-initio calculation of the Coulomb explosion of N_2 after heavy-ion bombardement

Self-consistent-field calculations for the total potential energy of highly ionized N_2 molecules are presented. We compare these calculations to the experimentally observed energy released in the Coulomb explosion of ionized N_2 molecules created after collision with fast heavy ions. The most important electronic states of the fragment ions are determined.

Relativistic effects in physics and chemistry of element 105. [Part] I.

A detailed study of the electronic structure and bonding of the pentahalides of group 5 elements V, Nb, Ta, and element 105, hahnium (and Pa) has been carried out using relativistic molecular cluster Dirac-Slater discrete-variational method. A number of calculations have been performed for different geometries and molecular bond distances. The character of the bonding has been analyzed using the Mulliken population analysis of the molecular orbitals. It is shown that hahnium is a typical group 5 element. In a great number of properties it continues trends in the group. Some peculiarities in the electronic structure of HaCl_5 result from relativistic effects.

Interpretation of the anisotropy of M MO radiation in slow I on Au collisions

A comparison between experimental and calculated spectral shape and energy dependence of the M MO x-ray anisotropy in heavy-ion collisions of I on Au is presented. The calculation is performed within the kinematic-dipole model of anisotropy using MO x-rays determined from SCF relativistic correlation diagrams.

Analysis of the electronic structure, hyperfine structure, and volume isotope shifts in the low lying states of BA I and BA II

Relativistic multi-configuration Dirac Fock (MCDF) wavefunctions coupled to good angular momentum J have been calculated for low lying states of Ba I and Ba II. These wavefunctions are compared with semiempirical ones derived from experimental atomic energy levels. It is found that significantly better agreement is obtained when close configurations are included in the MCDF wavefunctions. Calculations of the electronic part of the field isotope shift lead to very good agreement with electronic factors derived from experimental data. Furthermore, the slopes of the lines in a King plot analysis of many of the optical lines are predicted accurately by these calculations. However, the MCDF wavefunctions seem not to be of sufficient accuracy to give agreement with the experimental magnetic dipole and electric quadrupole hyperfine structure constants.

Solution of the Hartree-Fock equations for atoms and diatomic molecules with the finite element method

The finite element method (FEM) is now developed to solve two-dimensional Hartree-Fock (HF) equations for atoms and diatomic molecules. The method and its implementation is described and results are presented for the atoms Be, Ne and Ar as well as the diatomic molecules LiH, BH, N_2 and CO as examples. Total energies and eigenvalues calculated with the FEM on the HF-level are compared with results obtained with the numerical standard methods used for the solution of the one dimensional HF equations for atoms and for diatomic molecules with the traditional LCAO quantum chemical methods and the newly developed finite difference method on the HF-level. In general the accuracy increases from the LCAO - to the finite difference - to the finite element method.

Spin-polarized Hartree-Fock-Slater calculations in atoms and diatomic molecules with the finite element method

We present spin-polarized Hartree-Fock-Slater calculations performed with the highly accurate numerical finite element method for the atoms N and 0 and the diatomic radical OH as examples.

Electronic structure of UF_5

Non-relativistic and relativistic self-consistent Hartree- Fock-Slater and Dirac-Slater models have been used to calculate one-electron energy levels and ionization energies for UF_5. The calculations were performed in an assumed structure of C_4v symmetry with the uranium atom at the center of mass of the molecule. The spacing and level ordering are compared with earlier results obtained with the MS X\alpha method using the muffin-tin approximation. Connections with the multiphoton isotope separation scheme of UF_6 are discussed.

Volume isotope shifts in low lying transitions of Au I

Electronic factors in the volume isotope shift have been calculated in an ab initio way with the relativistic Dirac-Fock method for a number of different optical single/and two-photon transitions in Au I. The agreement with a semi-empirical method is within 10% for the resonance transition. For this one and a few other transitions the effect of core excitation has been analyzed with the Multi-configuration Dirac-Fock method as well, and it was found to reduce the electronic factor in the order of 5 %.

State-dependent volume isotope shifts of low-lying states of group-IIa and -IIb elements

Results of relativistic multiconfiguration Dirac-Fock calculations with an extended nucleus are used to analyze the volume isotope shifts of the resonance transitions in the group-IIa and -IIb elements as well as in Yb. This is done together with a review of the isotope shift theory, including a critical evaluation and comparison of the semiempirical calculation of volume isotope shifts commonly used today. Electronic factors F_i, proportional to differences of electronic densities over the nuclear volume, are discussed within various approximations and compared with experimental results.

State dependent volume isotope shift analysis of the low lying states of Ba I and Ba II

Relativistic multi-configuration Dirac-Fock wavefunctions, coupled to good angular momentum J, have been calculated for low lying states of Ba I and Ba II. The resulting electronic factors show good agreement with data derived from recent high-resolution laser spectroscopy experiments and results from a comparison of muonic and optical data.

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.