Abstract
First-principles calculations were conducted to examine the impact of three sulfonamide-containing molecules (H(4)N(2)O(2)S, CH(8)N(4)O(3)S, and C(2)H(2)N(6)O(4)S) adsorbed on the FAPbI(3)(001) perovskite surface, aiming to establish a significant positive correlation between the molecular structures and their regulatory effects on the perovskite surface. A systematic comparison was conducted to evaluate the adsorption stability of the three molecules on the two distinct surface terminations. The results show that all three molecules exhibit strong adsorption on the FAPbI(3)(001) surface, with C(2)H(12)N(6)O(4)S demonstrating the most favorable binding stability due to its extended frameworks and multiple electron-donating/withdrawing groups. Simpler molecules lacking carbon skeletons exhibit weaker adsorption and less dependence on surface termination. Ab initio molecular dynamics simulations (AIMD) further corroborated the thermal stability of the stable adsorption configurations at elevated temperatures. Electronic structure analysis reveals that molecular adsorption significantly reconstructs the density of states (DOS) on the PbI(2)-terminated surface, inducing shifts in band-edge states and enhancing energy-level coupling between molecular orbitals and surface states. In contrast, the FAI-terminated surface shows weaker interactions. Charge density difference (CDD) analysis indicates that the molecules form multiple coordination bonds (e.g., Pb-O, Pb-S, and Pb-N) with uncoordinated Pb atoms, facilitated by -SO(2)-NH(2) groups. Bader charge and work function analyses indicate that the PbI(2)-terminated surface exhibits more pronounced electronic coupling and interfacial charge transfer. The C(2)H(12)N(6)O(4)S adsorption system demonstrates the most substantial reduction in work function. Optical property calculations show a distinct red-shift in the absorption edge along both the XX and YY directions for all adsorption systems, accompanied by enhanced absorption intensity and broadened spectral range. These findings suggest that sulfonamide-containing molecules, particularly C(2)H(12)N(6)O(4)S with extended carbon skeletons, can effectively stabilize the perovskite interface, optimize charge transport pathways, and enhance light-harvesting performance.