System-environment interaction and ultrafast dynamical processes involving conical intersections

• Applicant: Professor Dr. Horst Köppel
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2006 to 2011
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 23385399

Conical intersections, a particular topology of intersecting electronic potential energy surfaces, play a key role in the photochemistry of many molecular systems, where they represent a paradigm for ultrafast internal conversion phenomena. While their impact on the quantum dynamics of small isolated species is well known, very few studies have been dedicated to large isolated polyatomic systems or system-environment complexes, where an intra or intermodular environment is expected to strongly influence the dynamics at conical intersections. This project focuses on methodological developments to describe the dynamics through conical intersections in macrosystems. These developments are based on two recent advances in the group: the elaboration of an effective-mode formulation, suitable to describe the short-time dynamics through conical intersections in macrosystems, and the derivation of an efficient way of constructing diabatic states appropriate for multidimensional quantum-dynamical calculations. It is the development and combination of these advances, to go for the first time to an accurate description of the quantum dynamics through conical intersections in macrosystems, which constitute the objectives of this project. Applications to challenging molecular systems are planned.

• DFG Programme: Research Grants