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Using ab initio nonadiabatic molecular dynamics, we study the effect of large A-site cations on nonradiative electron–hole recombination in two-dimensional Ruddlesden–Popper perovskites HA2APb2I7, HA = n-hexylammonium, A = methylammonium (MA), or guanidinium (GA). The steric hindrance created by large GA cations distorts and stiffens the inorganic Pb–I lattice, reduces thermal structural fluctuations, and maintains the delocalization of electrons and holes at ambient and elevated temperatures. The delocalized charges interact more strongly in the GA system than in the MA system, and the charge recombination is accelerated. In contrast, replacement of only some MA cations with GA enhances disorder and increases charge lifetime, as seen in three-dimensional perovskites. This study highlights the key influence of structural fluctuations and disorder on the properties of charge carriers in metal halide perovskites, providing guidance for tuning materials' optoelectronic performance. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting has been a focal point of research to solve energy and environmental issues. However, the understanding of photocatalytic water splitting and coupled dynamics of photogenerated charge carriers at molecule/semiconductor interfaces is still limited. We have combined ab initio molecular dynamics, real-time time-dependent density functional theory, and nonadiabatic molecular dynamics to study the dissociation of water and capture of photogenerated holes on the pristine rutile TiO2(110) surface. Our simulations indicate that intermolecular hydrogen bonding (IHB) between water molecules facilitates water dissociation. The dissociation energy of water molecules in a pristine, non-dissociated structure is reduced by 15%, from 0.26 eV to 0.21 eV, due to IHB. In the semi-dissociated structure, the dissociation energy of a water molecule is only 0.13 eV, owing to proton transfer induced by IHB. In the semi-dissociated structure, IHB between H2O and terminal hydroxyl (OtH) stabilizes the dissociated structure. Furthermore, IHB promotes spatial isolation of OtH and bridging hydroxyl (ObrH) and inhibits their recombination. The stabilized dissociated structure activates high-frequency vibrational modes that increase the nonadiabatic coupling and promote hole capture on a femtosecond timescale, accelerating the capture rate by 36%. The findings provide important insights into photo-dissociation of water on rutile TiO2(110), particularly shedding light on the impact of key intermediates on the photocatalytic process. [ABSTRACT FROM AUTHOR]

Extracting hot‐carriers before they relax back to the band edge will reduce thermal dissipation above the bandgap, which is one of the primary sources of efficiency loss in perovskite solar cells (PSCs). It requires slow cooling of hot‐carriers together with the efficient extraction of hot‐carriers. Here, a novel interface engineering is demonstrated by embedding radical‐containing nanographene (r‐NG●) between perovskite and poly[bis(4‐phenyl)(2,4‐dimethoxyphenyl)‐amine] (PTOAA) to harvest this excess energy. This strategy accelerates the extraction rate of the hot‐hole (3 times that of control at 400 K) by augmenting the relaxation channel, which is related to the "quasi‐SOMO" energy state of r‐NG●. Nonadiabatic molecular dynamics calculation further revealed that radical character promotes the rotation of the cation in perovskite, which contributes to generating strong nonadiabatic couplings and multiple phonon modes. In addition, the band bending effect of buried perovskite and improved conductivity of PTOAA also facilitate exciton dissociation and hole collection efficiency (97.5%). Consequently, the resultant r‐NG● decorated PSCs delivered an impressive efficiency of 24.20%, along with better thermal and humidity stability. Moreover, it can maintain 93% of its initial efficiency after 300 hours of illumination. [ABSTRACT FROM AUTHOR]