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Controlling ultrafast material transformations with atomic precision is essential for future nanotechnology. Pulsed laser annealing (LA), inducing extremely rapid and localized phase transitions, is a powerful way to achieve this but requires careful optimization together with the appropriate system design. We present a multiscale LA computational framework that can simulate atom-by-atom the highly out-of-equilibrium kinetics of a material as it interacts with the laser, including effects of structural disorder. By seamlessly coupling a macroscale continuum solver to a nanoscale superlattice kinetic Monte Carlo code, this method overcomes the limits of state-of-the-art continuum-based tools. We exploit it to investigate nontrivial changes in composition, morphology, and quality of laser-annealed SiGe alloys. Validations against experiments and phase-field simulations as well as advanced applications to strained, defected, nanostructured, and confined SiGe are presented, highlighting the importance of a multiscale atomistic-continuum approach. Current applicability and potential generalization routes are finally discussed., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz 2 GeBr 4 and PhBz 2 GeI 4 can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C 3 N 4 ) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

Tin-halide perovskites (THPs) have emerged as promising lead-free perovskites for photovoltaics and photocatalysis applications but still fall short in terms of stability and efficiency with respect to their lead-based counterpart. A detailed understanding of the degradation mechanism of THPs in a water environment is missing. This Letter presents ab initio molecular dynamics (AIMD) simulations to unravel atomistic details of THP/water interfaces comparing methylammonium tin iodide, MASnI 3 , with the lead-based MAPbI 3 . Our results reveal facile solvation of surface tin-iodine bonds in MASnI 3 , while MAPbI 3 remains more robust to degradation despite a larger amount of adsorbed water molecules. Additional AIMD simulations on dimethylammonium tin bromide, DMASnBr 3 , investigate the origins of their unprecedented water stability. Our results indicate the presence of amorphous surface layers of hydrated zero-dimensional SnBr 3 complexes which may protect the inner structure from degradation and explain their success as photocatalysts. We believe that the atomistic details of the mechanisms affecting THP (in-)stability may inspire new strategies to stabilize THPs.

Mn-doped lead halide perovskites exhibit long-lived dopant luminescence and enhanced host excitonic quantum yield. The contention between energy and charge transfer in sensitizing dopant luminescence in Mn-doped perovskites is investigated by state-of-the-art DFT calculations on APbX 3 perovskites (X = Cl, Br, and I). We quantitatively simulate the electronic structure of Mn-doped perovskites in various charge and spin states, providing a structural/mechanistic analysis of Mn sensitization as a function of the perovskite composition. Our analysis supports both energy- and charge-transfer mechanisms, with the latter probably preferred in Mn:CsPbCl 3 due to small energy barriers and avoidance of spin and orbital restrictions. An essential factor determining the dopant luminescence quantum yield in the case of charge transfer is the energetics of intermediate oxidized species, while bandgap resonance can well explain energy transfer. Both aspects are mediated by perovskite host band edge energetics, which is tuned in turn by the nature of the halide X., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Metal halide perovskites exhibit impressive optoelectronic properties with applications in solar cells and light-emitting diodes. Co-doping the high-band gap CsPbCl 3 perovskite with Bi and Mn enhances both material stability and luminescence, providing emission on a wide spectral range. To discuss the role of Bi 3+ and Mn 2+ dopants in tuning the CsPbCl 3 perovskite energy levels and their involvement in carrier trapping, we report state-of-the-art hybrid density functional theory calculations, including spin-orbit coupling. We show that co-doping the perovskite with Bi and Mn delivers essentially the sum of the electronic properties of the single dopants, with no significant interaction or the preferential mutual location of them. Furthermore, we identify the structural features and energetics of transitions of electrons trapped at Bi and holes trapped at Mn dopant ions, respectively, and discuss their possible role in determining the optical properties of the co-doped perovskite.

Tin halide perovskites make up the only lead-free material class endowed with optoelectronic properties comparable to those of lead iodide perovskites. Despite significant progress, the device efficiency and stability of tin halide perovskites are still limited by two potentially related phenomena, i.e., self-p-doping and tin oxidation. Both processes are likely related to defects; thus, understanding tin halide defect chemistry is a key step toward exploitation of this class of materials. We investigate the MASnI 3 perovskite defect chemistry, as a prototype of the entire materials class, using state-of-the-art density functional theory simulations. We show that the inherently low ionization potential of MASnI 3 is solely responsible of the high stability of tin vacancy and interstitial iodine defects, which are in turn at the origin of the material p-doping. Tin vacancies create a locally iodine-rich environment that could promote Sn(II) → Sn(IV) oxidation. The higher band edge energies of MASnI 3 compared to those of MAPbI 3 lead to the emergence of deep electron traps associated with undercoordinated tin defects (e.g., interstitial tin) and the suppression of deep transitions associated with undercoordinated iodine defects that are typical of MAPbI 3 . Thus, while lead iodide perovskites are dominated by iodine chemistry, tin chemistry dominates tin iodide perovskite defect chemistry. Mixed tin/lead perovskites exhibit an intermediate behavior and are predicted to be potentially free of deep traps. Compositional alloying with different metals is finally explored as a strategy for mitigating defect formation and self-p-doping in tin iodide perovskites.

Spin-forbidden reactions are frequently encountered when transition metal oxo species are involved, particularly in oxygen transfer reactivity. The computational study of such reactions is challenging, because reactants and products are located on different spin potential energy surfaces (PESs). One possible approach to describe these reactions is the so-called minimum energy crossing point (MECP) between the diabatic reactants and products PESs. Alternatively, inclusion of spin-orbit coupling (SOC) effects allows to locate a saddle point on a single adiabatic PES (TS SOC). The TS SOC approach is rarely applied because of its high computational cost. Recently evidence for a TS SOC impact on significantly lowering the activation barrier in dioxygen addition to a carbene-gold(I)-hydride complex reaction (Chem. Sci. 2016, 7, 7034-7039) or even on predicting a qualitatively different reaction mechanism in mercury methylation by cobalt corrinoid (Angew. Chem. Int. Ed. 2016, 55, 11503-11506) has been put forward. Using MECP and TS SOC approaches a systematic analysis is provided here of three prototypical transition metal oxo spin-forbidden processes to investigate their implications on reactivity. Cycloaddition of ethylene to chromyl chloride (CrO 2 Cl 2 +C 2 H 4 ), iron oxide cation insertion into the hydrogen molecule (FeO + +H 2 ) and H-abstraction from toluene by a Mn V -oxo-porphyrin cation (MnOP(H 2 O) + +C 6 H 5 CH 3 ) are case studies. For all these processes the MECP and TS SOC results are compared, which show that the spin-forbidden reactivity of transition metal oxo species can be safely described by a MECP approach, at least for the first-row transition metals investigated here, where the spin-orbit coupling is relatively weak. However, for the Mn-oxo reactivity, the MECP and TS SOC have been found to be crucial for a correct description of the reaction mechanism. In particular, the TS SOC approach allows to straightforwardly explore detailed features of the adiabatic potential energy surface which in principle could affect the overall reaction rate in cases where the involved diabatic PESs are tricky., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The Mn-oxo porphyrin (MnOP) mechanism for substrate hydroxylation is computationally studied with the aim to better understand reactivity in these systems. Theoretical studies suggest Mn(V)OP species to be very reactive intermediates with thermally accessible reaction barriers represented by low-spin/high-spin-crossover occurring in the Mn(V)OP oxidant, and kinetics for selected Mn(V)OP species indeed find high reactivity. On the other hand, MnOP complexes lead to modest yields in hydroxylation reactions of several different substrates, implying low rate constants and high reaction barriers. The resolution of this inconsistency is very important to understand the reactivity of Mn-oxo porphyrins and to improve the catalytic conditions. In this work we use the toluene hydroxylation by the Mn(V)OP(H 2 O) + complex as a case study to gain deep insight into the reaction mechanism. Minimum energy crossing point (MECP) results on the H-abstraction process from toluene indicate a first crossover from a singlet to a triplet spin state of the Mn(V)OP(H 2 O) + species with a thermally accessible barrier, followed by a very facile H-abstraction by the triplet complex. Issues concerning (i) the validation of the level of the density functional theory employed (BP86) to describe the singlet-triplet energy gap in the Mn(V)OP(H 2 O) + system versus highly accurate DMRG-CASPT2/CC calculations, and (ii) the influence of the axial ligand (X = none, Cl - , CH 3 CN, OH - , and O 2- ) on MnOP reactivity, which models the different experimental conditions, are addressed. The ligand trans influence mainly controls the reactivity through the singlet-triplet energy gap modulation, with the porphyrin ruffling distortion also finely tuning it. Finally, a stepwise model for the H-abstraction process is proposed which allows a direct comparison between the calculated and experimentally measured Gibbs free activation energy barriers ( Zhang et al. J. Am. Chem. Soc. 2005 , 127 , 6573 - 6582 ). The low yields in catalysis are shown not to be due to low reactivity of Mn(V).

Attaining the durability of high-efficiency perovskite solar cells (PSCs) operated under concomitant light and thermal stresses is still a serious concern before large-scale application. It is crucial to maintain the phase stability of the organic hole-transporting layer for thermostable PSCs across a range of temperatures sampled during device operation. To address this issue, we propose a racemic semiconducting glassy film with remarkable morphological stability, exemplified here by a low-molecular symmetry oxa[5]helicene-centered organic semiconductor (O5H-OMeDPA). The helical configuration of O5H-OMeDPA confers the trait of multiple-dimension charge transfer to the solid, resulting in high hole mobility of 6.7 × 10 -4 cm 2 V -1 s -1 of a solution-processed glassy film. O5H-OMeDPA is combined with a triple-cation dual-halide lead perovskite to fabricate PSCs with power conversion efficiencies of 21.03%, outperforming the control cells with spiro-OMeTAD (20.44%). Moreover, the cells using O5H-OMeDPA exhibit good long-term stability during full-sunlight soaking at 60°C., (Copyright © 2019 The Author(s). Published by Elsevier Inc. All rights reserved.)