Real-Time Propagation TDDFT and Density Analysis for Exciton Coupling Calculations in Large Systems

Photoactive systems are characterized by their capacity to absorb the energy of light and transform it. Usually, more than one chromophore is involved in the light absorption and excitation transport processes in complex systems. Linear-Response Time-Dependent Density Functional (LR-TDDFT) is commonly used to identify excitation energies and transition properties by solving the well-known Casida’s equation for single molecules. However, in practice, LR-TDDFT presents some disadvantages when dealing with multichromophore systems due to the increasing size of the electron–hole pairwise basis required for accurate evaluation of the absorption spectrum. In this work, we extend our local density decomposition method that enables us to disentangle individual contributions into the absorption spectrum to computation of exciton dynamic properties, such as exciton coupling parameters. We derive an analytical expression for the transition density from Real-Time Propagation TDDFT (P-TDDFT) based on Linear Response theorems. We demonstrate the validity of our method to determine transition dipole moments, transition densities, and exciton coupling for systems of increasing complexity. We start from the isolated benzaldehyde molecule, perform a distance analysis for π-stacked dimers, and finally map the exciton coupling for a 14 benzaldehyde cluster