Asymptotically forbidden quasimolecular optical transitions induced by low-temperature collisions

• Antragsteller: Professor Dr. Robert J. Buenker
• Fachliche Zuordnung: Theoretische Chemie: Elektronenstruktur, Dynamik, Simulation
• Förderung: Förderung von 2003 bis 2008
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 5411055

The project is aimed at investigating theoretically the optical collisions which lead to the formation of atoms in metastable states or the radiative depopulation of atomic metastable states in binary collisions at low temperatures. The project includes: 1) Ab initio calculations of the interaction energy surfaces and optical transition moments involved, with emphasis on the correct description of Rydberg orbitals and relativistic effects; 2) subsequent calculations of the spectral profiles for absorption/radiation, as well as angular distributions of atoms/molecules and total cross sections under optical collisions or radiative depopulation, with specific emphasis on the correct description of the coupling of the relative rotational motion of the two atoms and the electronic angular momentum in optical transitions as well as the non-Condon transitions; 3) the development of an analytical approach for the description of atom-diatomic molecule optical transitions in low temperature collisions, with specific emphasis on the isotopic effect in Hg-H2/D2 collisions; 4) the development of a semiclassical theory for intramultiplet transitions in optical collisions based on ab initio potential energy surfaces.

• DFG-Verfahren: Sachbeihilfen