A Computational Comparative Study for the Spectroscopic Evaluation of Triazine Derivative Dyes in Implicit Solvation Model Systems Using Semi-Empirical and Time-Dependent Density Functional Theory Approaches

Abstract

The spectroscopic data for a range of cyclopenta-[d][1,2,3]-triazine derivative dyes have been evaluated using various standard computational approaches. Absorption data of these dyes were obtained using the ZINDO/S semi-empirical model for vertical excitation energies of structures optimised with the AM1, PM3, and PM6 methods. These studies were conducted under vacuum and solution states using the polarisation continuum model (PCM) for implicit solvation in the linear response model. The accuracy, along with the modest computational costs of using the ZINDO/S prediction, combined with the PM3 optimisation method for absorption data was reliable. While a higher computational cost is required for the time-dependent density functional theory (TDDFT), this method offers a reliable method for calculating both the absorption and emission data for the dyes studied (using vertical and adiabatic excitation energies, respectively) via state-specific solvation. This research demonstrates the potential of computational approaches utilising solvation in evaluating the spectroscopic properties of dyes in the rational design of fluorescent probes.