Molecular modeling of mordant black dye for future applications as visible light harvesting materials with anchors: design and excited state dynamics

Abstract

In this study, new visible light harvesting dyes (MBR1-MBR5) have been designed as efficient materials with silyl based anchoring abilities on semiconducting units for future dye-solar cells applications. Their unique molecular structures of novel D-π-ASemiconductor typewere evaluated thoroughly by density functional theory (DFT) calculations. To enhance the optical performance in visible region, a novel dye structure (MBR) was derived from the chemical structure of mordant black (MB) dye with electron acceptor semiconducting units (MBR1-MBR5). The Coulomb-attenuating Becke, 3-parameter, Lee-Yang-Parr (CAM-B3LYP) functional, which had a hybrid and long-range correlation with 6-31G + (d,p), generated a [Formula: see text] (683nm) that was very comparable to its experimental value (672nm). The energies of highest occupied molecular orbitals (HOMO), lowest unoccupied molecular orbitals (LUMO), and their HOMO-LUMO energy gaps (HLG) were calculated. Their ionization potentials (IP) varied from 5.616 to 8.320eV, demonstrating their good electron donating trend. The [Formula: see text] values of dyes displayed a significant red shift from MBR (682nm) value with range 565-807nm except MBR1 which was slightly blue shifted. The dye MBR4, which had the smallest HLG (0.23eV) had the greatest second order nonlinear optical (NLO) response of 144,234 Debye-Angstrom-1. The DFT calculated results provided insight into the creation of new silyl anchoring groups for future DSSCs material designs with increased stability and effectiveness. The goal of the current study is to forecast the development of novel NLO materials with a D-π-ASemiconductor design that use semiconductors as anchoring groups to adhere to a surface.