Exploration of Pull-Push Effect for Novel Photovoltaic Dyes with A-π-D Design: A DFT/TD-DFT Investigation.

The π-rich versus π-poor units in 4,6-di(thiophen-2-yl)pyrimidine (DTB) alternating the π-backbone of solar cells dyes have been extended with a push-pull technique to lower their HOMO-LUMO energy gap and to increase Intramolecular Charge Transfer (ICT). Density functional theory was used to optimize the ground state molecular geometries of newly designed dyes (DTB1-DTB6). Time Dependent DFT (TD-DFT) was used to simulate the Uv-vis spectral values at the maximum absorbance values ranging between 481-535 nm. These values were red shifted from DTB value of experimental (333 nm) and theoretical (346 nm). however, their computed absorbance and fluorescence spectra revealed a bathochromic shift of them upon an increasing the solvent polarity. Different DFT functionals such as (B3LYP, CAM-B3LYP, B97XD, and APFD) were employed to choose their proper use Uv-visible analysis to reveal an unexpected coherence at the B3LYP level with experimental values. As a result, the B3LYP with most diffused basis sets of 6-31G + (d,p) were used for further calculations. The parameters of Global Chemical reactivities revealed that all the dyes had a softer nature with their softness value range of 0.27-0.41. their Ionization Potentials (IP) ranged between 6.21-8.10 eV to comply that the new dyes had good electron donating potentials. With a good electron injection potential of -1.47-1.74 eV, aluminum can be the best electrode, while Au is excellent towards a hole injection operation which had the potential range of 1.79-3.68 eV. For Natural Bond Orbital (NBO) assessment, (N14)LP → (F16-F28)π* with stabilization energy of 42.55 kcal/mol was noted for DTB4. Their Second order hyperpolarizability [Formula: see text] values as their Nonlinear Optical (NLO) response ranged between 59.16-232.11 debye-angstrom