We present an efficient real-time time-dependent density functional theory (TDDFT) method for large-scale accurate simulations of electron–nucleus dynamics, as implemented in the time dependent ab-initio package (TDAP). By employing a local basis-set presentation, we are able to simulate systems of large size (∼500 atoms) and for long electronic propagation time (∼300–500 fs) with less computation cost while maintaining relatively high accuracy.

We show several quintessential examples, such as photoabsorption spectra of dye-sensitized TiO2 nanowire, proton transfer coupled nonradiative relaxation of eumelanin constituents, electron injection and electron–hole recombination in dye solar cells, hole-transfer dynamics between MoS2/WS2 interlayer heterojunction, and solvent effects on electron dynamics. Our method is demonstrated to have superiority over available methods in dealing with interesting excited state characteristics of complex systems involving dynamics of electrons and atoms.

This paper was originally published in Computational Materials 112, Part B, (2016) 478–486


Recent progresses in real-time local-basis implementation of time dependent density functional theory for electron–nucleus dynamics