First‐principles dynamics of photoexcited molecules and materials towards a quantum description

The past decades have witnessed the success of ground‐state density functional theory capturing static electronic properties of various materials. However, for time dependent processes especially those involving excited states, real‐time time‐dependent density functional theory (rt‐TDDFT) and advanced nonadiabatic algorithms are essential, especially for practical simulations of molecules and materials under the occurrence of ultrafast laser field. Here we summarize the recent progresses in developing rt‐TDDFT approaches within numerical atomic orbitals and planewave formalisms, as well as the efforts combining rt‐TDDFT and ring polymer molecular dynamics to take into account nuclear quantum effects in quantum electronic‐nuclear dynamic simulations. Typical applications of first‐principles dynamics of excited electronic states including high harmonic generation, charge density wave, photocatalytic water splitting, as well as quantum nuclear motions in ozone and graphene, are presented to demonstrate the features and advantages of these methods. The progresses in method developments and practical applications provide unprecedented insights into nonadiabatic dynamics of excited states in the Ehrenfest scheme and beyond, towards a comprehensive understanding of excited electronic structure, electron–phonon interactions, photoinduced charge transfer and chemical reactions, as well as quantum nuclear motions in excited states. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Density Functional Theory Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods