Toolkits for simulation and interpretation of photoinduced processes: a mixed classical-quantum approach

Sapunar, Marin (2021) Toolkits for simulation and interpretation of photoinduced processes: a mixed classical-quantum approach. Doctoral thesis, Sveučilište u Zagrebu, Prirodoslovno-matematički fakultet.

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Abstract

Photochemical reactions involve multiple interacting electronic states which means they need to be treated using methods beyond the Born-Oppenheimer approximation. In the current work, contributions are made to mixed classical-quantum methods for studying these reactions. First, highly efficient numerical algorithms were developed to calculate overlap integrals between electronic wave functions at different nuclear configurations. These integrals are essential for nonadiabatic dynamics simulations at the mixed classical-quantum level but are also shown here to be very useful for facilitating the analysis of the electronic states in large ensembles of nuclear configurations. This type of analysis is then used to revisit two prototypical reactions in photochemistry, hydrogen dissociation in pyrrole and internal conversion in pyrazine. In pyrrole, the effect of Rydberg-valence mixing in the bright ππ∗ state on the time scale of the reaction is discussed. In pyrazine, the very early population of two nπ∗ states is conclusively proven

Item Type:	Thesis (Doctoral thesis)
Uncontrolled Keywords:	excited states; nonadiabatic dynamics; nuclear ensemble approach; pyrazine; pyrrole; wave function overlaps
Subjects:	NATURAL SCIENCES > Chemistry NATURAL SCIENCES > Chemistry > Physical Chemistry NATURAL SCIENCES > Chemistry > Theoretical Chemistry
Divisions:	Division of Physical Chemistry
Depositing User:	Marin Sapunar
Date Deposited:	06 Jul 2023 10:24
URI:	http://fulir.irb.hr/id/eprint/8082

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