We illustrate the effect of solvation on the nature of electronic excitations of organic molecules which possess excited states of charge-transfer character. The analysis is carried out using both a continuum model and a polarizable QM/MM method that treats the solvent atomistically and embeds each atom in the solvent with a fluctuating charge which responds to the solute quantum-mechanical electrostatic potential in a self-consistent manner. We also show how solvation dynamics can influence the nature of the excited state of molecular systems. The application of the model to aqueous solutions of doxorubicin and a substituted polythiophene derivative shows that the solvent significantly affects the nature the excited states, which results in an enhanced or reduced charge-transfer character as measured using two of the most popular indices for evaluating the distance traveled by the electrons upon excitation.

On the nature of charge-transfer excitations for molecules in aqueous solution: a polarizable QM/MM study

Egidi, Franco;LO GERFO, Giulia;Macchiagodena, Marina;Cappelli, Chiara
2018

Abstract

We illustrate the effect of solvation on the nature of electronic excitations of organic molecules which possess excited states of charge-transfer character. The analysis is carried out using both a continuum model and a polarizable QM/MM method that treats the solvent atomistically and embeds each atom in the solvent with a fluctuating charge which responds to the solute quantum-mechanical electrostatic potential in a self-consistent manner. We also show how solvation dynamics can influence the nature of the excited state of molecular systems. The application of the model to aqueous solutions of doxorubicin and a substituted polythiophene derivative shows that the solvent significantly affects the nature the excited states, which results in an enhanced or reduced charge-transfer character as measured using two of the most popular indices for evaluating the distance traveled by the electrons upon excitation.
Charge-transfer; QM/MM; Solvation; Physical and Theoretical Chemistry
File in questo prodotto:
File Dimensione Formato  
2018-CT-transitions-with-FQ.pdf

accesso aperto

Descrizione: post-print full text
Tipologia: Altro materiale allegato
Licenza: Non pubblico
Dimensione 13.55 MB
Formato Adobe PDF
13.55 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/74206
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 11
  • ???jsp.display-item.citation.isi??? 11
social impact