First principle investigation of new metal-free organic dye molecular for DSSCs: effects of π-conjugated groups

Abstract

ABSTRACT Based on 1-phenylpyrrolidine (PT) dye, six new metal-free organic molecules S1–S6, containing PT as donor (D) connected through different linkages (π) and cyanoacrylic acid as acceptor (A), were designed and studied for dye sensitised solar cells (DSSCs). In this paper, D-π-A system of S1–S6 dye molecules was investigated by quantum chemical calculations to inspect the optical absorption properties and photovoltaic (PV) parameters. In particular, there are applied three long-range corrected (LC) functionals, such as B3PW91, CAM-B3LYP and ωB97XD with the time-dependent DFT (TD-DFT) calculation to systematically investigate the absorption peak in PT dye. From the calculated results, CAM-B3LYP functional was a good match with the PT dye. Therefore, the S1–S6 molecules’ optical absorption spectra have been computed by using the CAM-B3LYP/6-31+G(d) theory. The conductor-like polarisable continuum model (C-PCM) results show that the precise absorption spectra have attained solvent effect included in the excited state geometries. The frontier molecular orbitals (FMOs) of the HOMOs and LUMOs energies of S1–S6 derivatives confirm positive results on the dye regeneration and electron injection processes. The outcomes display that the benzo[c][1,2,5]thiadizole (S4) and benzo[c][1,2,5]oxadizole (S5) molecules are the most suitable spacers for D to A, owing to longer absorption peaks and revealing red-shifted optical absorption.