<p>Time-dependent density functional theory (TDDFT) has been the most widely used quantum computational technique to calculate the electronic transition energies of both organic and inorganic molecules. Calculation of absorption maximum of organic molecules through TD-DFT and its comparison with the experimental values has been a challenge throughout. In this investigation, benchmarking of density functionals has been carried out with the objective of using TD-DFT approach for excited state calculations of triphenylamine (TPA) based D-π-A systems. TPA forms a major class of dyes investigated as sensitizers for dye-sensitized solar cells (DSSC). Bulk solvent effects have been modelled using polarizable continuum model (PCM). Solvent’s effect on calculated absorption maximum depending upon whether the solvent is included at the initial geometry optimization stage has also been studied. Eighteen different functionals from various rungs of Jacob’s ladder of density functionals, amounting to different values of Hartree-Fock Exchange (HFX) and the mean field Hartree-Fock method have been employed to model 46 TPA based D-π-A systems. Results show that the functionals with higher amount of HFX tend to perform better in calculation of the charge transfer excitation energy.</p> Graphical abstract <p>The graphical abstract illustrates a comparison between Hartree–Fock exchange (HFX) and density functional exchange (DFX) in hybrid functionals for accurately describing chargetransfer excitations in triphenylamine-based D–π–A molecular architectures. For well charge-separated systems, functionals containing a higher fraction of HFX generally exhibit better performance.</p> <p></p>