Abstract
Context Comparatively, metal-free sensitizers featuring the chalcogen family receive less attention despite known electronic properties for metal-chalcogenide materials. This work reports an array of optoelectronic properties using quantum chemical methods. Observed red-shifted bands within the UV/Vis to NIR regions with absorption maxima > 500 nm were consistent with increasing chalcogenide size. There is a monotonic down-shift in the LUMO and ESOP energy consistent with O 2p, S 3p, Se 4p, to Te 5p atomic orbital energies. Excited-state lifetime and charge injection free energies follow the decreasing order of chalcogenide electronegativity. Adsorption energies of dyes on TiO2 anatase (101) range between - 0.08 and - 0.77 eV. Based on evaluated properties, selenium- and tellurium-based materials show potential use in DSSCs and futuristic device applications. Therefore, this work motivates continued investigation of the chalcogenide sensitizers and their application. Methods The geometry optimization was performed at B3LYP/6-31 + G(d,p) and B3LYP/LANL2DZ level of theory for lighter and heavier atoms, respectively, using Gaussian 09. The equilibrium geometries were confirmed by the absence of imaginary frequencies. Electronic spectra were obtained at CAM-B3LYP/6-31G + (d,p)/LANL2DZ level of theory. Adsorption energies for dyes on a 4 x 5 supercell TiO2 anatase (101) were obtained using VASP. The dye-TiO2 optimizations were employed using GGA and PBE with the PAW pseudo-potentials. The energy cutoff was set at 400 eV and convergence threshold for self-consistent iteration was set to 10(-4), and van der Waals were accounted using DFT-D3 model and on-site Coulomb repulsion potential set at 8.5 eV for Ti.