Nuclear Quantum Effects Accelerate Charge Separation and Recombination in g-C₃N₄/TiO₂ Heterojunctions

We combined ring-polymer molecular dynamics (MD) and ab initio MD with nonadiabatic MD to study the effects of nuclear quantum effects (NQEs) on interlayer electron transfer and electron-hole recombination at the g-C₃N₄/TiO₂ interface. Our simulations indicate that NQEs significantly affect electron transfer and electron-hole recombination dynamics, accelerating both processes. NQEs deform the g-C₃N₄ layer and expedite the movement of carbon and nitrogen atoms, thus, enhancing charge delocalization and interlayer coupling. This improved overlap between electronic state wave functions enhances nonadiabatic couplings, facilitating electron transfer and recombination. In addition to the enhanced nonadiabatic couplings accelerating electron transfer, the presence of NQEs narrows the energy gap and delays decoherence by mitigating overall fluctuations, because of restricted TiO₂ movements overwhelming enhanced g-C₃N₄ fluctuations, thereby making the recombination faster. This work provides valuable insights into NQEs in light-element systems and contributes to guiding the development of highly efficient photocatalysts.