The proposed PhD in theoretical chemistry deals with the use of excited-state methods (TD-DFT, ADC(2), etc.) to explore the relationships between the molecular structures, photoinduced electron transfer (PeT), and chirality in strong connexion with the experimental groups in Bordeaux. Three main tasks will be carried out by the PhD student.

The PhD student will first focus on the selection and benchmarking of computational methodologies. During the first semseter, TD-DFT will be benchmarked against experimental and higher-level theoretical data. Ground-state structures will be optimized using various hybrid exchange-correlation functionals, and environmental effects will be investigated using both linear-response and state-specific solvation models to ensure accurate polarization effects.

In the second phase of the research, spanning months six to twenty-four, the student will work on establishing structure-property relationships for photoinduced electron transfer. This will involve correlating molecular architecture with electron transfer efficiency and comparing TD-DFT and Constrained DFT (C-DFT) to model charge transfer the relevant excited states. Electron transfer rates will be determined using Fermi’s Golden Rule scheme, incorporating vibronic coupling effects to gain a more quantitative understanding of these processes.

The final phase will focus on modelling chiral effects on electron transfer. A model approach describing chirality-induced effects on electron transfer will be developed and validated. The student will implement this approach, integrating spin-orbit coupling and vibronic effects to quantify the influence of chirality on electronic transitions.

This PhD is part of the ChiraPeT project (Deciphering the Influence of Chirality on Photoinduced Electron Transfer Processes), funded by the ANR. The project aims to develop novel molecular tools to investigate how chirality affects photoinduced electron transfer (PeT) in biomimetic systems across different time and length scales. The project employs precise molecular engineering to design chiral helical supramolecular architectures. These tailored compounds will enable the study of chiral effects on photoinduced processes at various timescales. The synergy between experimental and computational investigations, the latter being realized during the PhD, will provide new insights into long-range electron transfer in chiral molecular systems, ultimately advancing our understanding of the role of chirality in light-matter interactions within biological environments