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

• Final Report Year: 2017

Final Report Abstract

In this project we continued our study on the anionic states of large molecules, specifically on correlation bound anionic states. Early in the project, we discovered that the use of perturbation theory based ab initio methods do not deliver reliable results for anionic states where the anionic density overlaps with the neutral electrons and we therefore had to use the much more computationally demanding EOM-EA-CCSD. We have thoroughly explored the binding mechanism behind the multitude bound anionic states of the C60− anion. In our exploration, we have discovered two previously unknown bound anionic states and also demonstrated the effect of doping with noble gases on the C60− spectrum. We also developed a theoretical tool that would allow us to conclude that we have indeed discovered all of the bound anionic states of the C60− anion. Since we have focused our research on the anionic states of C60−, the originally planned study of large water clusters was not completed within the available time frame of the project. Two novel examples of electron-induced chemistry were further discovered which we believe open the door to a much broader, exciting, and so far unexplored chemistry. The density analysis tools developed during the project would also be invaluable in other systems and are thus an additional important contribution. We hope that the present research will stimulate future experimental and theoretical studies.

Publications

• A One-Step Four-Bond-Breaking Reaction Catalyzed by an Electron. Angew. Chem. Int. Ed. 2012, 51, 8003–8007
  D. Davis, V. P. Vysotskiy, Y. Sajeev, and L. S. Cederbaum
  
• Extreme Correlation Effects in the Elusive Bound Spectrum of C60−. J. Phys. Chem. Lett. 2013, 4, 3319
  S. Klaiman, E. V. Gromov, and L. S. Cederbaum
  
• All for one and one for all: accommodating an extra electron in C60. Phys. Chem. Chem. Phys. 2014, 16, 13287
  S. Klaiman, E. V. Gromov, and L. S. Cederbaum
  
• The best orbital and pair function for describing ionic and excited states on top of the exact ground state. J. Chem. Phys. 2014, 141, 194102
  S. Klaiman and L. S. Cederbaum
  
• Barrier-less single electron induced cis-trans isomerization. Angew. Chem. Int. Ed. 2015, 54, 10470–10473
  S. Klaiman and L. S. Cederbaum
  
• Influence of caged noble-gas atom on the superatomic and valence states of 𝐶60−. Molecular Physics 2015, 113 (19-20), 2964-2969
  E. V. Gromov, S. Klaiman, L. S. Cederbaum
  
• How many bound valence states does the C60− anion have? Phys. Chem. Chem. Phys. 2016, 18 (16), 10840-10845
  E. V. Gromov, S. Klaiman, L. S. Cederbaum