Chiariello, Maria Gabriella (2018) Models and Methods to understand ultrafast dynamics in photochemistry. [Tesi di dottorato]

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Item Type: Tesi di dottorato
Lingua: English
Title: Models and Methods to understand ultrafast dynamics in photochemistry
Creators:
CreatorsEmail
Chiariello, Maria Gabriellamariagabriella.chiariello@unina.it
Date: 9 January 2018
Number of Pages: 124
Institution: Università degli Studi di Napoli Federico II
Department: dep19
Dottorato: phd078
Ciclo di dottorato: 30
Coordinatore del Corso di dottorato:
nomeemail
Paduano, Luigiluigi.paduano@unina.it
Tutor:
nomeemail
Rega, NadiaUNSPECIFIED
Date: 9 January 2018
Number of Pages: 124
Uncontrolled Keywords: photochemistry; ab-initio dynamics; wavelet transform; vibrational analysis
Settori scientifico-disciplinari del MIUR: Area 03 - Scienze chimiche > CHIM/02 - Chimica fisica
Date Deposited: 24 Jan 2018 10:21
Last Modified: 14 Mar 2019 10:59
URI: http://www.fedoa.unina.it/id/eprint/12282

Abstract

The PhD project was devoted to the development and the validation of a general computational protocol for simulating and understanding ultrafast nuclear relaxation processes of chromophores upon interaction with light. Ab-initio molecular dynamics was employed in both the ground and excited electronic states of interest, to monitor the molecular response to the photoexcitation in real-time. Once representative trajectories have been collected, a multiresolution vibrational analysis based on the wavelet transform is performed. The far-from-equilibrium nuclear relaxation is therefore rationalized and understood in the frequency domain, maintaining the temporal information and providing a direct comparison with advanced time resolved vibrational spectroscopy experiments. The photoinduced relaxation of the pyranine photoacid molecule in aqueous solution was considered as first case study. As main finding, low frequency vibrational modes promoting photoreactivity are effectively individuated and correlated to key structural parameters of the relaxation process. Moreover, the modified reactivity of pyranine in presence of acetate was also investigated. We simulated the excited state proton transfer reactions (ESPT) involving pyranine-acetate and pyranine-water-acetate clusters in aqueous solution. The study has revealed interesting correlations between the structure of the reactive cluster and the ESPT kinetics, improving our understanding of the driving forces at the origin of ESPT photoreactivity. The last part of the thesis concerned the photoinduced reactivity of a diarylethene molecule, a well-known photo-switch system. In this case, the multiresolution vibrational analysis has been extended and tested to unveiling the anharmonic coupling between vibrational modes.

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