Weakly-bound and metastable anions: Developments of methods and applications

• Applicant: Professor Dr. Lorenz S. Cederbaum
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2005 to 2015
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 19719388

In the first stage of this project substantial progress has been made towards the theoretical study of large anions. A new massively parallel platform based on electron propagator theory (called P-RICD-Sigma) and a new complex absorbing potential which makes the calculations of metastable anionic states free of artificial resonances have been developed. We have demonstrated that the implemented second-order electron propagator method performs extremely well in comparasion with higher order coupled-cluster methods. The new class of correlation-bound anions has been introduced and characterized. A novel concerted elementary reaction mechanism has been discovered and named Bond Breaking by a Catalytic Electron (BBCE). The newly developed method and code have become a powerful tool to compute weakly-bound and metastable anions. We are now in the position to attack relatively large systems fully ab initio (which currently cannot be done otherwise), to solve controversial problems of current interest and to predict new binding mechanisms of an excess electron. The future project has mainly three objectives. The application of the method to water cluster anions is of relevance to the understanding of how water solvates electrons. The results are also needed to calibrate model potentials which can be used to study liquid water. Fullerene anions have been much studied in the literature. Whether a new class of anionic states (weakly-bound s-like states) exists and what properties they may have, has been discussed controversially. The application of the method developed can resolve the controversy fully ab initio. Moreover, the properties and prevailing binding mechanisms of these states can be determined. Last but not least, the method should be further developed and other interesting examples studied.

• DFG Programme: Research Grants