Theory of interatomic (intermolecular) Coulombic decay in clusters

• Applicant: Professor Dr. Lorenz S. Cederbaum
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2005 to 2011
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 19146214

Interatomic (intermolecular) Coulombic decay (ICD) is an extremely efficient decay mode of inner-valence-ionized states in clusters, which has been predicted theoretically by the applicant and co-workers [Phys. Rev. Lett. 79, 4778 (1997)]. Recently, the theoretical findings of the Heidelberg group have found their full confirmation in a series of spectacular ICD experiments [1, 3, 4]. While most of the theoretical work performed on ICD dealt with establishing the generality and the mechanism of the phenomenon, the recent experimental and theoretical progress opens new horizons for the ICD research. The present proposal is aimed to provide theoretical answers for the most important open questions in the field. Among these are:How can one accurately calculate total and partial ICD rates in polyatomic and molecular clusters?What is the dependence of an ICD rate on the relative orientation of two (or more) cluster subunits if one (or more) of these subunits is a molecule?What is the effect of nuclear dynamics on ICD in polyatomic and molecular clusters?What is the effect of relativity (e.g., spin-orbit coupling) on ICD?What interatomic (intermolecular) decay processes, apart from ICD, can be observed in clusters?In order to answer the above questions, we propose to significantly improve the existing ab initio methodology for the calculation of energies and decay rates of the relevant electronic states of the ionized clusters as functions of the cluster geometry. In particular, we shall use the Green¿s function approach for the calculation of the decay rates. The results of the proposed theoretical research will be essential for interpreting and guiding the future ICD experiments.

• DFG Programme: Research Grants