Quantum dynamics of highly-correlated electrons in molecules using the ML-MCTDH approach in second-quantization representation

• Applicant: Professor Dr. Oriol Vendrell
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 561888469

Understanding the dynamic properties of molecular aggregates and devices at the intersection of chemistry and materials science is increasingly important. This calls for theoretical methods that accurately model electronic structure and dynamics while remaining scalable, robust, and systematically convergent. This project will further extend and develop methods for first-principles descriptions of highly correlated electrons in molecules and aggregates. Our concept is to tackle these electronic dynamics leveraging the tools and methodologies from high-dimensional nuclear quantum dynamics, and adapting them to the different energy scale and structure of the problem. In doing so, we take advantage of the broad array of established electronic structure techniques to generate molecular orbitals and other intermediate quantities. To this end, we will develop algorithms that transform the molecular electronic Hamiltonian into forms suited for the multiconfiguration time-dependent Hartree method and its multilayer extension. Using a divide-and-conquer strategy, these algorithms will partition and compress the electronic Hamiltonian, enabling routine calculations in configuration spaces spanned by approximately 100 spatial molecular orbitals. With these advancements, we will investigate ultrafast charge separation in endohedral fullerenes such as Mg@Cn (n=20, 24, 60) and explore exciton and energy transport in aggregates of poly-conjugated organic molecules. Looking forward, we envision applications to organic-inorganic frameworks, which hold promise for energy and photovoltaic technologies.

• DFG Programme: Research Grants