The increasing need to simulate the dynamics of photoexcited molecular and nanosystems in the sub-picosecond regime demands new efficient tools able to describe the quantum nature of matter at a low computational cost. By combining the power of the approximate DFTB method with the semiclassical Ehrenfest method for nuclearelectron dynamics we have achieved a real-time time-dependent DFTB (TD-DFTB) implementation that fits such requierements. In addition to enabling the study of nuclear motion effects in photoinduced charge transfer processes, our code adds novel features to the realm of static and time-resolved computational spectroscopies. In particular, the optical properties of periodic materials such as graphene nanoribbons or the use of corrections such as the "LDA+U" and "pseudo SIC" methods to improve the optical properties in some systems, can now be handled at the TD-DFTB level.Moreover, the simulation of fully-atomistic time-resolved transient absorption spectra and impulsive vibrational spectra can now be achieved within reasonable computing time, owing to the good performance of the implementation and a parallel simulation protocol. Its application to the study of UV/visible light-induced vibrational coherences in molecules is demonstrated and opens a new door into the mechanisms of non-equilibrium ultrafast phenomena in countless materials with relevant applications.

The rational design of new materials as prototype systems for organic solar cells remains challenging. Perylene diimide has emerged as a promising material to replace fullerene derivatives because of its synthetic flexibility, leading to the manipulation of their optical properties. As a result of their fused aromatic core that favors π-π stacking interactions, the aggregation of these molecules can reach highly ordered nanostructures as one-dimensional nanofibers, with a fast photoinduced charge transfer mechanism. In this article, we present an atomistic description of the photoexcited exciton dynamics in noncovalently bonded perylene diimides by time integration of the electron density in the presence of external time varying electric fields. We show that our approach is able to capture and explain the physics that underlies the charge transport mechanism through perylene diimide aggregates.

For efficient conversion of light into useful energy sources, it is very important to study and describe the first steps of primary charge-transfer process in natural structures and artificial devices. The time scale of these processes in artificial photosynthetic and photovoltaic devices is on the order of femto- to picoseconds and involves vibronic coupling of electrons and nuclei and also nuclear alleviation to enhance charge separation. Here we present an atomistic description of the photoexcited electron dynamics in a noncovalently bonded system formed by an hydrogenated nanodiamond as donor and a perylene diimide as an acceptor. The complex shows extremely fast charge transfer, separation, and stabilization within 90 fs. This stabilization is purely electronic in nature. To the best of our knowledge, these results show for the first time that it is possible to stabilize charge without polaron formation or nuclear relaxation, reaching a steady state enhanced by a pure electronic reorganization.