Modeling the spectral properties of poly(x‐phenylenediamine) conducting polymers using a combined TD‐DFT and electrostatic embedding approach. Issue 30 (28th June 2022)

• Record Type: Journal Article
• Authors: Luise, Davide; D'Alterio, Massimo Christian; Talarico, Giovanni; Ciofini, Ilaria; Labat, Frédéric
• Is Part Of: Journal of computational chemistry. Volume 43:Issue 30(2022)
• Page Start: 2001
• Page End: 2008
• Publication Date: 2022-06-28
• Subjects: absorption spectra of polymers -- conductive polymers -- DFT and TD‐DFT -- embedding approaches; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26955
• Languages: English
• ISSNs: 0192-8651

Abstract

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 ( D CT ). 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. Abstract : The combination of periodic density functional theory with time‐dependent DFT calculations carried out on finite clusters embedded in a set of point charges devised to exactly reproduce the electrostatic potential of the periodic chains has been successfully applied to simulate the absorption spectra of a family of polymers.