Excited state energy surfaces of flexible emitters for thermally activated delayed fluorescence

Organic Light-Emitting Diodes (OLEDs) technology has matured over recent years, reaching the commercialization level and being used in various applications. The required efficiency can be achieved by transforming triplet excitons into singlet states via Reverse InterSystem Crossing (RISC), which a general mechanism called thermally activated delayed fluorescence (TADF). Two prototypical molecules in the field, 2CzBN and 4CzBN, Carbazole Benzonitrile (donor-acceptor) derivatives, possess similar energy gap between singlet and triplet (∆EST, a key parameter in the RISC rate), but different TADF performance. In this sense, other parameter must be considered to explain these different behaviors. In this work, we theoretically investigate 2CzBN and 4CzBN and address the problem of how flexible donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) molecular architectures affect the nature of excited state, and the oscillator strength. Furthermore, we analyze the RISC rates as a function of the conformation of the carbazole side groups, considering the S0, S1, T1 and T2 states. The oscillator strength of 4CzBN is higher than of 2CzBN, which, in turn, is almost vanishing, resulting in only 4CzBN being a TADF active molecule. We also note the presence of a second triplet state T2 lower in energy than S1, and that the reorganization energies, associated to the RISC processes involving T1 and T2, are both important factor in differentiating the rates in 2CzBN and 4CzBN. However, the 4CzBN RISC rate from T2 to S1 is surprisingly high with respect to the one from T1 to S1, although, according to EL-Sayed rules, since T2 (CT/LE) is more similar to S1 (CT) than in 2CzBN (LE, CT), this transition should be less favored. These insights are important to understand the photophysics of the TADF process and to design novel TADF emitters based on the benzo-carbazole architecture.

Study of the rotational state of Titan using radio tracking data of the Dragonfly mission

Our solar system contains an impressive amount of celestial bodies. For example Saturn posses a huge variety of natural satellites, the diversity in size and physical proprieties of which might amaze imagination. The observational data gathered in 30 years range of deep space missions revealed, that some of these bodies can hide subsurface oceans under their crust. The water, as we know, serves as a fundamental base for a possible appearance of life. This statement is quite exited for the scientific society and serves as a reason for studying so called ”ocean worlds”. In order to detect the celestial bodies with the hidden subsurface ocean, one of the key aspects is the study of their rotational state, which is strongly coupled with the body internal structure. It can be done through the various techniques mentioned in Chapter 1. The main goal of the thesis is the study of rotational state of Titan, whose interior structure expectedly contains liquid ocean layer under its icy crust. Titan is the largest moon of Saturn and it is the second largest moon in the solar system in general. This natural satellite is of particular scientific interest, because it is one of a kind which has substantial atmosphere. The present work was done using radio tracking data of the Dragonfly mission which is one of the next NASA’s missions destined for Titan selected as a part of the New Frontiers Program in 2019. The detailed characteristic of the Dragonfly regarding the landing site and mission lifetime was reported in Chapter 2. The radio-tracking communication link from Titan side was performed using Dragonfly X band transponder according to the schedule tracking opportunity. From Earth side according to the mission, Deep Space Station 25 which is a part of NASA’s Deep Space Network was considered. Only Doppler data was used for studying Titan rotational state, even though there are other reliable techniques described in Chapter 3, that in general could be implemented.

Analisi energetica al variare dello state of charge di propulsori ibridi e plug-in operanti nel ciclo WLTP con propulsore termico a punto fisso stechiometrico

Il presente lavoro propone la stesura di un codice in ambiente MATLAB per l'analisi energetica di powertrain ibridi operanti nel ciclo WLTP con il particolare funzionamento del motore termico benzina a punto fisso stechiometrico. Nello specifico, il codice prende dei dati in input tramite un'interfaccia grafica ed avvia una simulazione, i cui risultati principali corrispondono ad emissioni di anidride carbonica per chilometro percorso ed ai chilometri percorsi con un litro di carburante. Queste sono le due grandezze che questo lavoro si prefigge di ottimizzare, dalle quali proviene la scelta del particolare funzionamento del motore termico. Sono state implementate due differenti strategie di controllo, una generale ed una più particolare. La simulazione con la strategia generale è stata applicata a tre differenti scenari reali, con le caratteristiche tecniche di tre veicoli realmente esistenti che vengono inserite nell'interfaccia grafica. I risultati provenienti da queste simulazioni sono stati poi analizzati e discussi nel dettaglio, anche con l'ausilio di grafici a supporto della spiegazione. La strategia di controllo particolare non è stata applicata a scenari reali ma ha portato alla definizione di una ipotetica architettura di powertrain ibrido, alla quale la sopracitata strategia si adatta al meglio. Dopo aver proposto miglioramenti e possibili ulteriori sviluppi di questo lavoro, sono state tratte le conclusioni generali, allargando il tutto al contesto più ampio in cui si va ad inserire.