PhD defense, Francesco Talotta (LCPQ), december 2018

Titre : Excited-state mechanisms and dynamics of the ruthenium nitrosyl complex trans-[RuCl(NO)(Py)4]2+

Presentation During this PhD thesis, we have carried out a series of theoretical studies of the photochemistry of the ruthenium nitrosyl complex trans-[RuCl(NO)(Py)4]2+. In particular, in the first part of my defence, I will present the results of accurate ab initio calculations such as CASSCF/CASPT2, that shed light on the role of the excited states, highlighting the possibility of several photoisomerization pathways. The main IC and ISC pathways will be discussed, along with the spin-orbit couplings responsible for the ISC transitions. In the second part I will present the results of the full dimensional surface hopping dynamics, including the description of non-adiabatic and spin-orbit couplings. These results will confirm the assumptions of the ab-initio calculations. I will present an accurate estimation of the branching ratio between the different photoisomerization pathways, together with the identification of the most important quenching funnels that slow down the entire N→O isomerization process.

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