Faraday Discussions最新文献

{"title":"Spiers Memorial Lecture: The Seven Samurai of sustainable electrochemicals: a systems perspective on power-to-X.","authors":"André Bardow","doi":"10.1039/d6fd00134c","DOIUrl":"https://doi.org/10.1039/d6fd00134c","url":null,"abstract":"<p><p>While molecular breakthroughs in power-to-X technologies continue to advance rapidly, their translation into large-scale industrial climate victories remains strikingly limited, even for energy carriers and platform chemicals that allow the substitution of identical fossil molecules. In this Perspective, we adopt the cinematic metaphor of Akira Kurosawa's <i>Seven Samurai</i> to demonstrate that molecular chemistry cannot defend our sustainability goals in isolation. We establish seven non-negotiable systems criteria that must be satisfied simultaneously: (1) thermodynamic limits, (2) actionable process gaps against state-of-the-art benchmarks (<i>e.g.</i>, electro-methanol), (3) paired anodic/cathodic synthesis, (4) thermal/pressure process integration, (5) opportunity costs against alternative net-zero baselines (<i>e.g.</i>, direct air capture and storage), (6) integration into a circular technology portfolio, and (7) planetary boundary constraints. We argue that real-world system viability is strictly multiplicative; if any single criterion fails, overall impact collapses to zero. Finally, we highlight that technology alone cannot bypass Earth system limits, necessitating a shift toward service-level demand sufficiency. To maximize its impact on real-world defossilisation, we encourage the electrochemistry community to look beyond active catalyst sites to create products that are fundamentally better than 1 : 1 fossil replacements and master the full-system requirements of sustainable chemical manufacturing.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149316134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unified adiabatic and diabatic excited-state description <i>via</i> the ensemble-variational quantum eigensolver.","authors":"Christophe Soule, Bruno Senjean, Benjamin Lasorne","doi":"10.1039/d6fd00064a","DOIUrl":"10.1039/d6fd00064a","url":null,"abstract":"<p><p>Within the present noisy intermediate-scale quantum-computing era, hybrid quantum-classical-processor algorithms have emerged as promising avenues for tackling electronic-structure eigenproblems. Among them, the so-called ensemble-variational quantum eigensolver has been designed to treat ground and excited states on an equal footing and proven effective in capturing features such as conical intersections and avoided crossings between two electronic states, as we recently demonstrated for formaldimine. We also showed in that example how the underlying ensemble-variational principle was prone to providing a quasi-diabatic representation \"for free\". To date, this method has been limited to computing only two eigenstates of a Hamiltonian. The aim of the present paper is to show how and under what conditions this can be generalized to models that involve three or more coupled electronic states. Our approach relies on designing a parameterized basis transformation that can directly be implemented on a quantum computer for further post-treatment. This nontrivial step is accompanied by the development of quantum circuits specifically adapted to the several states of interest. An algebraic optimization strategy for the parameters of the basis transformation is formulated to obtain the target eigenstates as well as the optimally diabatic states under various objective flavors of the ensemble-variational principle. Our approach was tested for addressing the first three coupled electronic states of the H+4 molecular ion as a proof of principle, with three electrons in four spatial orbitals, along various geometries.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149293319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational design and modelling of next generation optoelectronic materials: general discussion.","authors":"Rakesh Agrawal, Pol Benítez, Esmée Berger, Keith T Butler, Claudio Cazorla, Romain Claes, Andrea Crovetto, Mirjana Dimitrievska, David Fermin, Erik Fransson, Alex M Ganose, Diego A Garzón, James D Green, Anat Itzhak, Rafael Jaramillo, Prakriti Kayastha, Linn Leppert, Igal Levine, José A Márquez, Robert W Martin, Lena A Mittmann, Clara Brendstrup Møller, Andrea Peluso, James Quirk, Adrian Romaniuk, Susan Schorr, Byungha Shin, M Chiara Spadaro, Jonathan Staaf Scragg, Dedi Sutarma, Thomas Unold, Lucy Whalley, Julia Wiktor, Ruiqi Wu, Andriy Zakutayev","doi":"10.1039/d6fd90036d","DOIUrl":"10.1039/d6fd90036d","url":null,"abstract":"","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"127-163"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Octahedral tilting in halide double perovskites: disentangling lone-pair chemistry and geometric effects.","authors":"Mehmet Baskurt, Erik Fransson, Madeleine Lindvik, Paul Erhart, Julia Wiktor","doi":"10.1039/d6fd00014b","DOIUrl":"10.1039/d6fd00014b","url":null,"abstract":"<p><p>Halide double perovskites (HDPs) have emerged as promising alternatives to their lead-based counterparts. However, their structural dynamics is less explored than that of conventional halide perovskites. In this work, we investigate octahedral tilting at 0 K and the relative stability of tetragonal and cubic phases of a set of 57 HDPs. By combining structural and energetic descriptors with simple geometric metrics, we identify the main trends controlling the stabilization of one-tilt tetragonal phases across this family. We find that both the magnitude of the tilt angles and the energetic preference for tilted phases correlate primarily with the Goldschmidt tolerance factor <i>t</i>. The presence of ns² lone-pair cations also correlates with enhanced tilting; however, this trend largely reflects that lone-pair chemistries in HDPs occur together with ionic sizes that shift <i>t</i> away from unity. Consistent with this picture, we observe several compounds without lone pairs that nonetheless exhibit strong octahedral tilting. Finally, using machine-learned interatomic potentials, we connect the 0 K tilting energetics to finite-temperature behavior: compounds with more strongly stabilized tilt phases exhibit higher transition temperatures, and phonon spectra at 350 K reveal soft and broad modes that are consistent with the trends in tolerance factors, tilt angles, and tilt energies at 0 K. Our results provide a systematic reference for structure-stability relationships in HDPs and clarify that lone-pair chemistry is correlated with, rather than the primary cause of, octahedral tilting.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"28-41"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13392922/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148560205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling the tunable transient optical response of colloidal 2D Mo_1-<i>x</i>W_<i>x</i>S₂ nanosheets.","authors":"Markus Xemaire, Timo Braun, Marco Kögel, Onno Strolka, Dominik A Rudolph, Jannik C Meyer, Jannika Lauth","doi":"10.1039/d6fd00079g","DOIUrl":"10.1039/d6fd00079g","url":null,"abstract":"<p><p>Understanding the excited state dynamics of colloidal transition metal dichalcogenides (TMDCs) is vital for advancing their tunable optical properties toward innovative photonic and electro-optic applications. Upon photoexcitation, alloyed TMDCs exhibit strong exciton-phonon coupling and an associated band gap renormalization (BGR), which is characterized by a pronounced red-shift of the transient absorption (TA) of the materials and which is <i>e.g.</i> highly interesting for signal modulation. Here, we characterize a series of colloidal semiconducting alloyed Mo_1-<i>x</i>W_<i>x</i>S₂ (<i>x</i> = 0, 0.5, 1) nanosheets (NSs) with mono- to few-layer thickness and ∼14 nm lateral size by femtosecond broadband TA spectroscopy. Our analysis allows for the probing of composition-dependent optical changes within Mo_1-<i>x</i>W_<i>x</i>S₂ alloys directly in solution. By changing the molybdenum to tungsten ratio in the synthesis, it is possible to tune the absorption of the A exciton between 614 and 655 nm. We treat the complicated combination of spectrally overlapping sub-picosecond up to microsecond persisting transients in TA spectra by targeted global analysis for the in depth interpretation of charge carrier recombination processes in alloyed Mo_1-<i>x</i>W_<i>x</i>S₂ NSs. We find our model to be particularly well suited for describing the probed decays over a wide temporal range and extract constants spanning from hot charge carrier interactions (0.6-0.8 ps) over exciton-phonon coupling and BGR (29-61 ps) to band gap recombination (2-6 ns) up to trapping of charge carriers (0.6-1.6 µs) respectively. These values indicate that colloidal Mo_1-<i>x</i>W_<i>x</i>S₂ NS alloys are indeed promising for an optical signal modulation by BGR, which is tunable in wavelength (614-655 nm), transient red shift (18-27 eV) and timescale, while solution-processability provides maximum flexibility.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"218-231"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148519602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Concluding remarks: Emerging materials for optoelectronics applications.","authors":"Andriy Zakutayev","doi":"10.1039/d6fd00131a","DOIUrl":"10.1039/d6fd00131a","url":null,"abstract":"<p><p>This paper offers a personal perspective on the 2026 <i>Faraday Discussions</i> meeting on emerging materials for optoelectronics applications. Common themes of the meeting included hybrid perovskites, BaZrS₃ and related chalcogenide materials, low-dimensional materials, and data-driven science including self-driving laboratories and accelerated calculations. Discussion highlights included debate on which properties should be measured or calculated for emerging materials, the role of impurities and approximations, and the balanced interface point between theory and experiment for the case of emerging materials for optoelectronics applications. The paper also considers a possible definition of an emerging material for optoelectronics applications. It reflects on lessons learned from working in emerging materials, including the importance of pursuing open problems, articulating the result significance clearly, and sharing both positive and negative results. In addition, it provides a perspective on the role of AI in emerging materials research. It offers a personal view on how <i>Faraday Discussions</i> can both benefit from and contribute to AI-enabled science, while preserving the central role of human discussion and reasoning. This paper is adapted from a transcript of the concluding remarks made at the meeting.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"530-538"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomic structure and structural disorder <i>vs.</i> device efficiency in Kesterite monograin solar cells with S/(S + Se) ≈ 0.8.","authors":"G Gurieva, K Ernits, D Sheptyakov, A Manjon Sanz, M Kirkham, M Avdeev, N Siminel, D Meissner, S Schorr","doi":"10.1039/d6fd00010j","DOIUrl":"10.1039/d6fd00010j","url":null,"abstract":"<p><p>Cu-poor/Zn-rich Cu₂ZnSn(S,Se)₄ (CZTSSe) monograins with S/(S + Se) = 0.8 were investigated using neutron powder diffraction to directly quantify Cu/Zn disorder and intrinsic point defects. According to their chemical composition, the monograins show a mixture of the off-stoichiometry types A and B. Monograins with a predominantly A-type off-stoichiometry exhibit reduced Cu/Zn disorder and increased V_Cu concentrations, whereas Zn_Sn defect concentration increases with increasing B-type off-stoichiometry. Zn_Cu antisite defects, belonging to both A and B off-stoichiometry types, increase with increasing deviation from stoichiometry, and the combined defect concentration is lowest towards the stoichiometric point and A-type line, correlating with highest photovoltaic efficiency. Opposing trends are observed between optical band gap and solar cell stability, indicating that monograin solar cells with the same anion ratio but lower band gap energy are more stable. By correlating the atomic-scale defect scenario to macroscopic device performance, these results provide a quantitative framework for defect engineering in kesterite-type absorbers.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"305-320"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148429518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of S source on BaZrS₃ crystallization at low temperatures: H₂S <i>vs.</i> elemental S.","authors":"Anat Itzhak, Lena Mittmann, Eugène Bertin, Inês Diogo, Andrea Crovetto","doi":"10.1039/d6fd00039h","DOIUrl":"10.1039/d6fd00039h","url":null,"abstract":"<p><p>Chalcogenide perovskites, particularly BaZrS₃, hold great promise for optoelectronic applications. Lowering the synthesis temperature of high-quality BaZrS₃ films has been a long pursuit that has recently yielded significant progress. However, achieving reproducible, device-grade films at moderate temperatures below 600 °C remains a significant challenge. This difficulty is primarily driven by three limiting factors that conventionally hinder BaZrS₃ crystallization: the formation of deep binary thermodynamic sinks, the inherently low atomic mobility of Zr ions, and competing reactions with O. In this work, we use a two-step process of reactive sputtering and post-annealing to demonstrate that the choice of S source in the first step dictates the crystallization pathway in the second. A directional evaporated S₂ beam provides a high chemical potential, which effectively suppresses O incorporation, but risks trapping the system in a rigid intermediate phase. In contrast, diffuse H₂S gas is likely to supply additional kinetic energy to the growing film through energetic ion bombardment. This promotes intimate atomic mixing within the amorphous precursor, bypassing binary phase separation and enabling crystallization in the subsequent post-annealing step even in the presence of O. Ultimately, the diffuse H₂S route decouples perovskite crystallization from the need for S-rich intermediate phases, while the directional beam creates a highly S-rich environment directly within the sputtering process. Both methods offer practical approaches to integrating these materials into optoelectronic devices by crystallizing films at 600 °C and potentially below, each with distinct advantages.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"192-205"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148467984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Clever materials: when models identify good materials for the wrong reasons.","authors":"Kevin Maik Jablonka","doi":"10.1039/d6fd00024j","DOIUrl":"10.1039/d6fd00024j","url":null,"abstract":"<p><p>Machine learning can accelerate materials discovery. Models perform impressively on many benchmarks. However, strong benchmark performance does not imply that a model has learned chemistry. I test a concrete alternative hypothesis: that property prediction can be driven by bibliographic confounding. Across five tasks spanning MOFs (thermal and solvent stability), perovskite solar cells (efficiency), batteries (capacity), and TADF emitters (emission wavelength), models trained on standard chemical descriptors predict author, journal, and publication year well above chance. When these predicted metadata (\"bibliographic fingerprints\") are used as the sole input to a second model, performance is sometimes competitive with conventional descriptor-based predictors. These results show that many datasets do not rule out non-chemical explanations of success. Progress requires routine falsification tests (<i>e.g.</i>, group/time splits and metadata ablations), datasets designed to resist spurious correlations, and explicit separation of two goals: predictive utility <i>versus</i> evidence of chemical understanding.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"464-478"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148429437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On the possibility of hybrid chalcogenide perovskite photovoltaics.","authors":"Ruiqi Wu, J J Acton, Shirui Wang, Alex M Ganose","doi":"10.1039/d6fd00025h","DOIUrl":"10.1039/d6fd00025h","url":null,"abstract":"<p><p>Chalcogenide perovskites are an emerging class of photovoltaic absorbers offering stable, lead-free structures and promising optoelectronic properties. To date, the literature on chalcogenide perovskites has focused primarily on fully inorganic systems such as BaZrS₃. This contrasts with the halide perovskites, for which hybrid organic-inorganic systems exhibit record performance. In this work, we assess the viability of hybrid chalcogenide perovskite absorbers using first-principles calculations. We screen a wide range of monovalent and divalent organic cations within the A-site to evaluate their electronic, optical, and thermodynamic properties. Our analysis reveals that the majority of candidates are structurally unstable; however, we identify the hydrazinium cation (N₂H₆²⁺) as a unique candidate that maintains a stable perovskite structure. Specifically, we identify N₂H₆ZrSe₃ as the most promising candidate, exhibiting a quasi-direct band gap of 1.31 eV and a theoretical maximum efficiency of 24.5% for a 200-nm thin film. This study represents the first comprehensive computational report on hybrid chalcogenide perovskites, opening new avenues for the development of Earth-abundant photovoltaic materials.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":"77-94"},"PeriodicalIF":3.1,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13719144/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148434409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}