The absorption spectra of polymers derived from ortho, meta and para phenylenediamines (o-PDA, m-PDA and p-PDA) have been simulated combining periodic density functional theory (DFT) calculations with time-dependent DFT simulations. These latter have been carried out on finite clusters embedded in a set of point charges devised to exactly reproduce the electrostatic potential of the periodic chains. The results are compared with those obtained for solvated o-PDA, m-PDA and p-PDA oligomers of increasing sizes extracted from the periodic structures. The electronic transitions involved have been investigated by a qualitative analysis based on isodensity maps completed by a quantitative analysis based on the density-based index (DCT). For poly-(o)- and poly-(p)- phenylenediamines the agreement with the experimental data is achieved already by modeling solvated dimers whereas the inclusion of long-range electrostatic effects is mandatory for poly-(m)-phenylenediamine highlighting the importance of an accurate treatment of the electrostatic environment when a finite cluster approach is considered.

Modeling the spectral properties of poly(x-phenylenediamine) conducting polymers using a combined TD-DFT and electrostatic embedding approach / Luise, D.; D'Alterio, M. C.; Talarico, G.; Ciofini, I.; Labat, F.. - In: JOURNAL OF COMPUTATIONAL CHEMISTRY. - ISSN 0192-8651. - 43:30(2022), pp. 2001-2008. [10.1002/jcc.26955]

Modeling the spectral properties of poly(x-phenylenediamine) conducting polymers using a combined TD-DFT and electrostatic embedding approach

D'Alterio M. C.;Talarico G.;
2022

Abstract

The absorption spectra of polymers derived from ortho, meta and para phenylenediamines (o-PDA, m-PDA and p-PDA) have been simulated combining periodic density functional theory (DFT) calculations with time-dependent DFT simulations. These latter have been carried out on finite clusters embedded in a set of point charges devised to exactly reproduce the electrostatic potential of the periodic chains. The results are compared with those obtained for solvated o-PDA, m-PDA and p-PDA oligomers of increasing sizes extracted from the periodic structures. The electronic transitions involved have been investigated by a qualitative analysis based on isodensity maps completed by a quantitative analysis based on the density-based index (DCT). For poly-(o)- and poly-(p)- phenylenediamines the agreement with the experimental data is achieved already by modeling solvated dimers whereas the inclusion of long-range electrostatic effects is mandatory for poly-(m)-phenylenediamine highlighting the importance of an accurate treatment of the electrostatic environment when a finite cluster approach is considered.
2022
Modeling the spectral properties of poly(x-phenylenediamine) conducting polymers using a combined TD-DFT and electrostatic embedding approach / Luise, D.; D'Alterio, M. C.; Talarico, G.; Ciofini, I.; Labat, F.. - In: JOURNAL OF COMPUTATIONAL CHEMISTRY. - ISSN 0192-8651. - 43:30(2022), pp. 2001-2008. [10.1002/jcc.26955]
File in questo prodotto:
Non ci sono file associati a questo prodotto.

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: https://hdl.handle.net/11588/889813
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 4
  • ???jsp.display-item.citation.isi??? 3
social impact