A Combined Theoretical and Experimental Study of FEMTOsecond Bio-mimetic Photo-SWITCHes – Towards Rational Design Principles

• Applicant: Dr. Oleg Kornilov
• Subject Area: Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: since 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 545673796

The main objective of the FEMTO-Switch project is establishing rational grounds for chemical structure controls of molecular energetics and excited state dynamics at important conical intersections (key areas in the potential energy landscape of a molecule) ultimately determining the reaction quantum yields of ultrafast photo-switches based on C=C double bond isomerization. As the molecular platform for these investigation two molecular scaffolds are chosen: oxindole and oxopyrrole derivatives. The spectroscopic tools employed on the project involve ultrafast methods of transient absorption spectroscopy, fluorescence up-conversion spectroscopy and time-resolved photoelectron spectroscopy in liquid phase, complemented by advanced quantum chemistry calculations. To achieve the overarching goal the project consortium will work towards four research objectives: which are rooted in the expertise of the project partners and their pre-existing joint research: 1) Implementation of chemical substitutions of the oxindole (OxI) and oxopyrrole (OxP) platforms, which have a significant effect on the isomerization speed, the occurrence of a vibrational coherently driven reaction, and on the reaction quantum yields (QY). 2) Direct experimental observation of the energy landscape around the CIs of both type of switches by fs-PES in liquid phase. 3) Elucidation of the mechanisms which induce and preserve vibrational coherence for "ballistic" isomerisation, by combining fs-PES studies and UV/VIS/NIR transient absorption spectroscopy with sub-15-fs resolution, with multi-trajectory computations. 4) Development of the state-of-the-art quantum chemistry computations, which will explore efficient computational protocols, and strategies for computing experimental observables so as to rationalize the observed influence of chemical substitutions and solvent environment on ultrafast dynamics and reaction yields.

• DFG Programme: Research Grants
• International Connection: France
• Partner Organisation: Agence Nationale de la Recherche / The French National Research Agency
• Cooperation Partners: Professor Dr. Stefan Haacke; Miquel Huix-Rotllant, Ph.D.