Ab initio quantum dynamics of charge carriers in graphitic carbon nitride nanosheets

Graphitic carbon nitride (g-C₃N₄), a metal-free and visible light responsive photocatalyst, has garnered much attention due to its wide range of applications. In order to elucidate the role of dimensionality on the properties of photo-generated charge carriers, we apply nonadiabatic (NA) molecular dynamics combined with time-domain density functional theory to investigate nonradiative relaxation of hot electrons and holes, and electron-hole recombination in monolayer and bulk g-C₃N₄. The nonradiative charge recombination occurs on a nanosecond timescale and is faster in bulk than the nanosheet, in agreement with the experiment. The difference arises due to the smaller energy gap and participation of additional vibrations in the bulk system. The long carrier lifetimes are favored by small NA coupling and rapid phonon-induced loss of quantum coherence between the excited and ground electronic states. Decoherence is fast because g-C₃N₄ is soft and undergoes large scale vibrations. The NA coupling is small since electrons and holes are localized on different atoms, and the electron-hole overlap is relatively small. Phonon-driven relaxation of hot electrons and holes takes 100-200 fs and is slightly slower at higher initial energies due to participation of fewer vibrational modes. This feature of two-dimensional g-C₃N₄ contrasts traditional three-dimensional semiconductors, which exhibit faster relaxation at higher energies due to larger density of states, and can be used to extract hot carriers to perform useful functions. The ab initio quantum dynamics simulations present a comprehensive picture of the photo-induced charge carrier dynamics in g-C₃N₄, guiding design of photovoltaic and photocatalytic devices.