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Bolzonello, Luca (2016) Ultrafast relaxation dynamics of multichromophoric systems through advanced optical spectroscopies. [Ph.D. thesis]

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Abstract (english)

The light-matter interaction is one of the most interesting phenomena occurring in Nature. The interaction with light provides energy to the molecules, which is then released in the process of relaxation. This thesis deals with the investigation of relaxation mechanisms of molecules from a semi-quantum point of view. The use of quantum mechanics models is necessary to understand the operations and the results of advanced optical spectroscopies, such as 2D electronic spectroscopy, used precisely for the study of excitation and relaxation of molecules. The study and characterization of relaxation processes is of crucial importance to devise strategies to exploit and gain energy from them. Relaxation, as widely known, is strongly influenced by the surroundings and by the vibrations of the molecules. Therefore, we compared the relaxation dynamics of two systems with very different couplings with the environment. The first are aggregates of porphyrins that have weak coupling with the environment. However, it will be shown that the excitation is coupled with low frequency vibrations. The second is a quadrupolar system studied in its monomeric and dimeric form in different solvents. Surprisingly, a strong coupling between the dye transitions and a vibration of the solvent molecules was found. If confirmed, this effect could lead to new strategies for engineering light harvesting systems.

Abstract (italian)

L’interazione luce-materia è sicuramente uno dei più interessanti fenomeni in Natura. L’interazione con la luce fornisce energia alle molecole, che viene poi rilasciata nel processo di rilassamento. Questa tesi tratta meccanismi di rilassamento di molecole da un punto di vista semi-quantomeccanico. Questa trattazione è necessaria per comprendere il funzionamento e i risultati di spettroscopie ottiche avanzate, come la spettroscopia ottica 2D, utilizzate appunto per lo studio dell’eccitazione e del rilassamento delle molecole. Lo studio e la caratterizzazione di processi di rilassamento è di fondamentale importanza per ideare strategie per sfruttare il rilassamento al fine di ricavare parte dell’energia. Rilassamento che, come è noto, è fortemente influenzato dall'intorno e dalle vibrazioni delle molecole. Si sono quindi confrontate le dinamiche di rilassamento di due sistemi caratterizzati da accoppiamenti con l’intorno molto diversi. Il primo sistema considerato sono aggregati di porfirine che hanno uno scarso accoppiamento con l’intorno. Tuttavia si dimostrerà invece che tali sistemi sono caratterizzati da un forte accoppiamento con vibrazioni a bassa frequenza. Il secondo invece è un sistema quadrupolare del quale si studiano sia il monomero che il dimero in solventi diversi. Sorprendentemente si è trovato un forte accoppiamento delle molecole con una vibrazione del solvente, che se si dimostrerà vera, potrebbe aprire a nuove strategie per l’ingegnerizzazione di sistemi di light harvesting.

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EPrint type:Ph.D. thesis
Tutor:Collini, Elisabetta
Ph.D. course:Ciclo 28 > Scuole 28 > SCIENZE MOLECOLARI > SCIENZE CHIMICHE
Data di deposito della tesi:29 January 2016
Anno di Pubblicazione:29 January 2016
Key Words:2DES, 2DPE, vibronic coupling, quantum coherences
Settori scientifico-disciplinari MIUR:Area 03 - Scienze chimiche > CHIM/02 Chimica fisica
Struttura di riferimento:Dipartimenti > Dipartimento di Scienze Chimiche
Codice ID:9370
Depositato il:24 Oct 2016 14:47
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