Weak Donor-Acceptor Interaction and Interface Polarization Define Photoexcitation Dynamics in the MoS2/TiO2 Composite: Time-Domain Ab Initio Simulation.

To realize the full potential of transition metal dichalcogenides interfaced with bulk semiconductors for solar energy applications, fast photoinduced charge separation, and slow electron-hole recombination are needed. Using a combination of time-domain density functional theory with nonadiabatic molecular dynamics, we demonstrate that the key features of the electron transfer (ET), energy relaxation and electron-hole recombination in a MoS2-TiO2 system are governed by the weak van der Waals interfacial interaction and interface polarization. Electric fields formed at the interface allow charge separation to happen already during the photoexcitation process. Those electrons that still reside inside MoS2, transfer into TiO2 slowly and by the nonadiabatic mechanism, due to weak donor-acceptor coupling. The ET time depends on excitation energy, because the TiO2 state density grows with energy, increasing the nonadiabatic transfer rate, and because MoS2 sulfur atoms start to contribute to the photoexcited state at higher energies, increasing the coupling. The ET is slower than electron-phonon energy relaxation because the donor-acceptor coupling is weak, rationalizing the experimentally observed injection of primarily hot electrons. The weak van der Waals MoS2-TiO2 interaction ensures a long-lived charge separated state and a short electron-hole coherence time. The injection is promoted primarily by phonons within the 200-800 cm-1 range. Higher frequency modes are particularly important for the electron-hole recombinations, because they are able to accept large amounts of electronic energy. The predicted time scales for the forward and backward ET, and energy relaxation can be measured by time-resolved spectroscopies. The reported simulations generate a detailed time-domain atomistic description of the complex interplay of the charge and energy transfer processes at the MoS2/TiO2 interface that are of fundamental importance to photovoltaic and photocatalytic applications. The results suggest that even though the photogenerated charge-separated state is long-lived, the slower charge separation, compared to the electron-phonon energy relaxation, can present problems in practical applications.