Non-Hermitian Quantum Mechanics in Electronic-Structure Theory

• Applicant: Professor Dr. Thomas-Christian Jagau
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2017 to 2020
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 387825248

The goal of the research is to establish non-Hermitian quantum mechanics as a powerful and versatile tool in quantum chemistry. Novel wave-function based electronic-structure methods shall be developed that will enable the treatment of electronic resonances, that is, solutions of the time-independent Schrödinger equation with complex energy, in close analogy to bound states. These theoretical developments shall be combined with efficient computer code implementations and computational studies. Four main research directions are proposed: 1) characterization of the complex-valued potential energy surfaces (CPES) of polyatomic temporary radical anions, both on the basis of the Franck-Condon principle and beyond the Franck-Condon region by studying nuclear dynamics on CPES; 2) development and application of electronic-structure methods for autoionizing species with different electronic structure than radical anions, in particular Feshbach resonances and closed-shell dianions; 3) development and application of electronic-structure methods for molecular strong-field ionization and high-harmonic generation, in particular investigation of field-induced changes in molecular structure and properties; 4) modeling charge transport through molecular junctions within the quasistatic approximation by means of source-sink potentials. The research will exploit for the first time the remarkable isomorphism between these phenomena, i.e., that they are all governed by electronic resonances, and make them amenable to high-accuracy quantum-chemical calculations. In this way, a better understanding of a variety of questions that are not answered in a satisfactory way by currently available theoretical approaches will be gained. Respective areas of application are, for example, dissociative electron attachment, molecular high-harmonic generation, and the conductance of single molecules.

• DFG Programme: Independent Junior Research Groups
• Major Instrumentation: Rechnerverbund
• Instrumentation Group: 7070 Arbeitsplatzrechner, Personalcomputer