Relativistic Electronic Structure Theory and Its Applications to Chemical Reactions

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1. For the electronic structure calculations for molecules containing heavy atoms, an efficient spin-orbit (SO) CI method was formulated and implemented in the Columbus program system. For the efficient calculations, various group theories, such as unitary group, time-reversal symmetry, and double point group have been employed. SO interactions have been included in the SCF and MCSCF methods and the programs have been used to analyze the LS and jj coupling schemes in various atoms and cations.2. Photodissociation of Cl_2 molecule has been studied with the SOCI method and a Rosen-Zener-Demkov type non-adiabatic interaction at about R=6 bohr was found to be responsible for the wavelength dependence of the product branching ratio, anisotropy parameter, and quantum mechanical interference of the orientation of angular momentum j=l/2 of the product Cl(^2P_<1/2>) atom.3. Vibrational and rotational absorption intensities of the O_2 Herzberg band have been studied by the SOCI method with the theoretically obtained electronic transition moments and L-uncoupling matrix elements. In spite of the very weak intensities, fairly good agreement with experimental data was obtained. As for the anisotropy parameter, our data support the experimental results of Parker et al. The branching ratios of the products were determined by the multi-level and multi-step non-adiabatic interactions at longer bond distances.4. We have also studied theoretically on Icl, I^-_3, Xe+I_2, HgCO, HgAr, lanthanide cations, and transition metal-benzene complexes and so on.