A density functional study of thorium tetrahalides

The results of a study on the ground states of thorium tetrahalides using d ensity functional theory are presented. The equilibrium geometries of ThX4 (X=F, Cl, Br, I) have been optimized and their harmonic frequencies have be en calculated. In the geometry optimizations the results were generated by using two different density functional programs, namely GAUSSIAN98 and MAGI C. Both local and non-local functionals were used. This allowed us to bench mark the MAGIC program and check the consistency of the theoretical predict ions between different codes. Equilibrium structures, harmonic frequencies and zero-point energies were then calculated for a wider range of methods u sing GAUSSIAN98. Among these methods Hartree-Fock and Moller-Plesset second -order perturbation theory are included. All the calculated results are com pared with experimental values where available. The frequencies of only the nu(3) and nu(4) vibrational modes have been measured for ThF4 and only nu( 3) has been measured for ThCl4, while no vibrational frequencies have been measured for ThBr4 and ThI4. It is thus important to obtain improved values for all the vibrational frequencies of these molecules. Comparison can the n be made with existing values, most of which have been derived from empiri cal correlations with results from related lighter tetrahalide molecules.