A computer-algebraic approach to the study of the symmetry properties of molecules and clusters

This thesis work is dedicated to use the computer-algebraic approach for dealing with the group symmetries and studying the symmetry properties of molecules and clusters. The Maple package Bethe, created to extract and manipulate the group-theoretical data and to simplify some of the symmetry applications, is introduced. First of all the advantages of using Bethe to generate the group theoretical data are demonstrated. In the current version, the data of 72 frequently applied point groups can be used, together with the data for all of the corresponding double groups. The emphasize of this work is placed to the applications of this package in physics of molecules and clusters. Apart from the analysis of the spectral activity of molecules with point-group symmetry, it is demonstrated how Bethe can be used to understand the field splitting in crystals or to construct the corresponding wave functions. Several examples are worked out to display (some of) the present features of the Bethe program. While we cannot show all the details explicitly, these examples certainly demonstrate the great potential in applying computer algebraic techniques to study the symmetry properties of molecules and clusters. A special attention is placed in this thesis work on the flexibility of the Bethe package, which makes it possible to implement another applications of symmetry. This implementation is very reasonable, because some of the most complicated steps of the possible future applications are already realized within the Bethe. For instance, the vibrational coordinates in terms of the internal displacement vectors for the Wilson's method and the same coordinates in terms of cartesian displacement vectors as well as the Clebsch-Gordan coefficients for the Jahn-Teller problem are generated in the present version of the program. For the Jahn-Teller problem, moreover, use of the computer-algebraic tool seems to be even inevitable, because this problem demands an analytical access to the adiabatic potential and, therefore, can not be realized by the numerical algorithm. However, the ability of the Bethe package is not exhausted by applications, mentioned in this thesis work. There are various directions in which the Bethe program could be developed in the future. Apart from (i) studying of the magnetic properties of materials and (ii) optical transitions, interest can be pointed out for (iii) the vibronic spectroscopy, and many others. Implementation of these applications into the package can make Bethe a much more powerful tool.

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.