Exploring the effects of mono-bromination on hole-electron transport and distribution in dibenzofuran and dibenzothiophene isomers: a first-principles study

• Published in: Journal of molecular modeling 2024-06, Vol.30 (6), p.171-171, Article 171
• Main Authors: Deepakvijay, K., Prakasam, A.
• Format: Article
• Language: English
• Subjects: absorption; Absorption spectra; Bromination; Bromine; Characterization and Evaluation of Materials; Charge transport; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; computer software; Density functional theory; dibenzofuran; Dibenzothiophene; Donors (electronic); Electron transport; energy; Energy levels; First principles; Isomers; Molecular Medicine; Molecular orbitals; Molecular structure; Original Paper; polymers; Software packages; Theoretical and Computational Chemistry; Transport properties; wavelengths
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-024-05966-5

Context This study delves into hole-electron transport and distribution properties inherent in mono-brominated dibenzofuran (DBF) and dibenzothiophene (DBT) isomers. As determined by frontier molecular orbitals, all brominated structures have narrower bandgaps than their primary structures. The TD-DFT calculation showed that 2BDBT had the highest absorption wavelength of all molecules at 315.35 nm. Notably, the study unveils remarkably low electron and hole reorganization energies due to bromine substitution in DBF and DBT molecules. Specifically, the 4BDBF has the lowest hole reorganization energy of all DBF configurations, 0.229 eV. In addition, 3BDBF has 0.226 eV less electron reorganization energy than all other molecules. Compared to DBT, 3BDBT has the lowest electron reorganization energy of 0.254 eV. Overall, this research sheds significant light on the fundamental electronic and hole transport characteristics of bromine-substituted DBF and DBT isomers, highlighting their promising role in polymer design as donors/acceptors for advanced organic electronic applications. Methods Molecular structures were optimized using Density Functional Theory (DFT) B3LYP/6-311 +  + G (d, p) level of theory, and the study further elucidates these molecules’ energy levels and absorption spectra through Time-Dependent Density Functional Theory TD-DFT; these calculations were performed using Gaussian 09W software package. The key parameters such as reorganization energies, Electron Localization Function map, Laplacian Bond Order, and NCI-RDG were meticulously examined for the molecules with the results of DFT calculations were analyzed and displayed by utilizing the software packages VMD 1.9.4 and Multiwfn 3.8, aiming to comprehend their charge transport and distribution properties.