: Photoinduced electron transfer (ET), hole transfer (HT), charge recombination (CR) and energy transfer (EET) are fundamental mechanisms, which occur in both natural and artificial light harvesting systems. Here, we present a computational strategy which determines ET, HT, CR and EET rates in a consistent way and merges them in a kinetic model to reproduce the net excited state dynamics. The effects of the solvent are included in all steps of the calculations making the present strategy a useful tool for a rational design of charge and energy transfer processes in complex systems. An application to covalently linked zinc and free-base porphyrin-naphthalenediimide dyads is presented. For each of the two systems, ultrafast optical spectroscopy experiments have shown a specific photophysics with different processes taking place simultaneously. The model reveals that such a diversity is mainly due to the different relative stability of the charge-separated state, while the electronic couplings for charge and energy transfer processes are quite similar in the two dyads.
Electron and excitation energy transfers in covalently linked donor–acceptor dyads: mechanisms and dynamics revealed using quantum chemistry
Giannini, SamueleSecondo
;
2017
Abstract
: Photoinduced electron transfer (ET), hole transfer (HT), charge recombination (CR) and energy transfer (EET) are fundamental mechanisms, which occur in both natural and artificial light harvesting systems. Here, we present a computational strategy which determines ET, HT, CR and EET rates in a consistent way and merges them in a kinetic model to reproduce the net excited state dynamics. The effects of the solvent are included in all steps of the calculations making the present strategy a useful tool for a rational design of charge and energy transfer processes in complex systems. An application to covalently linked zinc and free-base porphyrin-naphthalenediimide dyads is presented. For each of the two systems, ultrafast optical spectroscopy experiments have shown a specific photophysics with different processes taking place simultaneously. The model reveals that such a diversity is mainly due to the different relative stability of the charge-separated state, while the electronic couplings for charge and energy transfer processes are quite similar in the two dyads.File | Dimensione | Formato | |
---|---|---|---|
Cupellini, Giannini, Mennucci - 2018 - Electron and excitation energy transfers in covalently linked donor–acceptor dyads mechanisms (2).pdf
solo utenti autorizzati
Tipologia:
Versione Editoriale (PDF)
Licenza:
NON PUBBLICO - Accesso privato/ristretto
Dimensione
2.31 MB
Formato
Adobe PDF
|
2.31 MB | Adobe PDF | Visualizza/Apri Richiedi una copia |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.