Effects of substituent groups and solvent media on Pyrene in ground and excited states: A DFT and TDDFT study

• Published in: Computational and theoretical chemistry 2015-03, Vol.1056, p.11-18
• Main Authors: Örücü, Hümeyra, Acar, Nursel
• Format: Article
• Language: English
• Subjects: Density functional theory; Intramolecular charge transfer; Pyrene; Pyrene derivatives; Time-dependent density functional theory
• ISSN: 2210-271X
• DOI: 10.1016/j.comptc.2015.01.001

[Display omitted] •Substituted Pyrene derivatives motivate new design for accurate photosensitive materials.•DFT and TDDFT studies of Pyrene and its derivatives have been investigated in gas phase and in solvents.•1-Pyreneaniline has intramolecular charge transfer between HOMO–LUMO at S1 excited state. This study presents a computational investigation of Pyrene and its –OH, –NH2, –CN, –CH2NH2, and –C6H5NH2 substituted derivatives in gas phase and different solvents. The calculations were performed using density functional theory (DFT) at rB3LYP/6-31G(d,p) level of theory for 1-substituted Pyrene derivatives. Excited state properties of molecules were obtained by time-dependent density functional theory (TDDFT). Molecular structure of the compounds, electronic and solvation energies, electronic transitions and HOMO–LUMO energy gaps were analyzed and compared using electron donor and electron acceptor substituents in gas phase and in solution. The results showed that the stability of the investigated systems increased with increasing solvent polarity. Analyses of the first excited singlet states revealed that there were slight charge transfers between substituent and Pyrene except for 1-Hydroxypyrene and 1-Aminopyrene. Among all the studied molecules, 1-Pyreneaniline is determined to be the best candidate for investigating and designing organic photosensitive materials with its high absorption intensity and charge transfer character.