ACS Physical Chemistry Au最新文献

{"title":"Ultrafast Spectroscopy with an Edge─Basic Concepts and Tabletop Applications of Femtosecond X-ray Transient Absorption Spectroscopy: A Tutorial Review","authors":"Caleb H. DeWitt,&nbsp;Aditi Bhattacherjee","doi":"10.1021/acsphyschemau.6c00024","DOIUrl":"10.1021/acsphyschemau.6c00024","url":null,"abstract":"<p>Electronic absorptionspectroscopy tools have long been part ofthe arsenal of molecular spectroscopy techniques to investigate theproperties of valence electrons and chemical bonds. However, in recentyears, this toolkit has rapidly expanded into the shallow and innercore orbitals, permitting a nuanced understanding of reaction dynamicsin excited electronic states from the vantage points of distinct atomicsites. As these tools continue to be innovated, particularly in tabletopimplementations, we provide an overview of how such versatile lightpulses are (i) generated and (ii) applied in basic research laboratories,not only to answering long-standing questions in molecular spectroscopybut also to tackling emerging problems in energy conversion and quantuminformation science. In this tutorial review, we dive into a conceptualunderstanding of how femtosecond extreme-ultraviolet and soft X-raypulses provide mechanistic understanding of ultrafast chemical dynamicsthrough tracking wide regions of the molecular phase space with atomic-sitefidelity. We further explain the nuts and bolts of a typical tabletopapparatus that control the parameters that determine the spectraland temporal resolution from the experimentalist’s standpoint.Finally, we circle back to spectroscopic selection rules from first-principles,connecting to several benchmark studies where femtosecond time-resolvedX-ray absorption spectroscopy provides a cutting “edge”in the real-time mapping of nonadiabatic processes that operate faraway from chemical equilibrium. Potential pitfalls and complementarymethodologies that map other details of the evolution of electronicand nuclear structures on ultrafast time scales are discussed.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 4","pages":"597–632"},"PeriodicalIF":4.8,"publicationDate":"2026-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148585439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Balanced Impurity and Interfacial Effects in La-Loaded ZrS2/CoxNiyO(OH)z Create Key Characteristics for Photocatalytic Water Splitting in DFT Simulation","authors":"Joran Celis,&nbsp;Aku Lempelto,&nbsp;Wei Cao","doi":"10.1021/acsphyschemau.5c00128","DOIUrl":"10.1021/acsphyschemau.5c00128","url":null,"abstract":"<p>Water splitting photocatalystscan be tracked in first-principlessimulation. This involves probing versatile series of changes to atomisticmodels until the calculated properties morph to perfection. In thisarticle, a design process as such unfolds. First, a prescriptive guidelineis derived to obtain semiconductive derivatives of the CoO₂ monolayer. This inspires the drawing of a set of bilayers consistingof CoO₂ on ZrS₂, with H, La, and Ni impurities.Precisely tuned redox potentials and a supportive built-in electricfield manifest in DFT simulations when these impurities are balancedin appropriate ratios. It is shown how charge redistributions andthe formed interlayer and intralayer dipoles underpin this outcome.The LaZr₁₆S₃₂/Co₁₄Ni₁₄O₄₅(OH)₁₁ bilayer is identified as a promisingwater splitting photocatalyst. The system is remarkable because ofits polarized semihybridized single-gap electronic structure. Initialprospects on mechanistic properties are also provided, suggestingthat 3Ni-coordinated oxygen promotes water splitting through enhancedvacancy formation. The work provides conceptual enrichment for anyresearcher in the field of photocatalysis.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"435–445"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acidic pH Modulates Headgroup Orientation and Packing in Bis(monoacylglycero)phosphate Bilayers","authors":"Tayana Mazin Tsubone,&nbsp;Pedro Nunes de Oliveira Junior,&nbsp;Gustavo Scanavachi,&nbsp;Vinicius Firmino dos Santos,&nbsp;Antonio Rodrigues da Cunha,&nbsp;Ana Paula Ramos,&nbsp;Thereza A. Soares,&nbsp;Rosangela Itri","doi":"10.1021/acsphyschemau.5c00150","DOIUrl":"10.1021/acsphyschemau.5c00150","url":null,"abstract":"<p>Bis(monoacylglycero)phosphate (BMP) possesses an atypicalheadgroupstructure, and its naturally occurring 2,2′-isomer rapidlyrearranges to the more stable 3,3′-form in aqueous buffers.Because the BMP is a major component of endosomal and lysosomal membranes,understanding its intrinsic physicochemical behavior is broadly relevantto the organization of acidic intracellular interfaces. To quantifyhow acidity modulates the physicochemical organization of 3,3′-BMPmembranes, we characterized model bilayers across a controlled pHrange by using electrophoretic mobility, fluorescence spectroscopy,optical microscopy, small-angle X-ray scattering (SAXS), dynamic lightscattering (DLS), and atomistic molecular dynamics (MD) simulations.Below pH 5, BMP vesicles show a marked decrease in surface charge,a reduction in area per lipid, and diminished hydration at the polar–apolarinterface. Simulations reveal that protonation enables transient flippingof the phosphate group toward the hydrophobic core, generating a pH-dependentcoexistence of headgroup orientations absent in the deprotonated state.Experimentally, these changes manifest as reduced vesicle sizes andthe emergence of multilamellar protrusions and locally folded membraneregions. The combined results demonstrate how small variations inthe BMP charge state generate amplified structural responses at thebilayer level, establishing a molecular mechanism by which protonationgoverns packing, hydration, and curvature in BMP-rich membranes.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"483–492"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heavy Water Remodels the DNA Energy Landscape to Stabilize Folded States and Slow Transitions","authors":"Sung Eun Kim,&nbsp;Hyeon-Min Moon,&nbsp;Il-Buem Lee,&nbsp;Kwang Hyun Cho,&nbsp;Changbong Hyeon,&nbsp;Seok-Cheol Hong","doi":"10.1021/acsphyschemau.5c00139","DOIUrl":"10.1021/acsphyschemau.5c00139","url":null,"abstract":"<p>Heavy water (D₂O) subtly strengthens hydrogenbonds,yet its full biological impact has remained fragmentary and controversial.Here we present an integrated, multi-scale study showing that D₂O consistently fortifies DNA while dampening life processes.From bulk <em>Escherichia coli</em> (<em>E. coli</em>) cultures to PCR assays, circular dichroism melting,FRET measurements, and single-molecule force spectroscopy, every methodconverges on the same picture: replacing H₂O with D₂O stabilizes both canonical duplexes and noncanonical i-motifstructures, elevates thermal and mechanical thresholds for strandseparation, and translates into markedly slower bacterial growth.Notably, our first direct measurements of hairpin unzipping and refoldingforces in heavy water show that deuterium-enhanced hydrogen bonding─ratherthan D₂O’s higher viscosity─dominates theslowdown of DNA-related transitions, deepening the folded-state wellwhile only modestly stabilizing intermediates. A minimal quantum-mechanicalanalysis attributes this trend to reduced zero-point energies of hydrogen-bondvibrations upon H → D substitution. This coherence across independenttechniques clarifies longstanding inconsistencies surrounding heavy-watereffects and nucleic-acid mechanics. By showing how isotopic substitutionreshapes the DNA energy landscape, our work provides a quantitativefoundation for future studies that exploit deuterium to probe or controlbiomolecular function.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"451–461"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Leaving-Group Effects in SN2@P: Potential Energy Surface and Dynamics of the F– + PH2I Reaction Compared to Its Cl–-Leaving-Group Analogue","authors":"Laura C. Erdei,&nbsp;Dóra Papp,&nbsp;Gábor Czakó","doi":"10.1021/acsphyschemau.6c00016","DOIUrl":"10.1021/acsphyschemau.6c00016","url":null,"abstract":"<p>We investigate thedynamics of the F^– + PH₂I reaction usingthe quasi-classical trajectory method ona newly developed ab initio analytical potential energy surface, witha special focus on stereoselectivity and leaving-group effects bycomparing to previous F^– + PH₂Cl results.Besides the overall more exothermic energy profile, the S_N2 pathway of the F^– + PH₂I reactionis found to be more indirect, with vibrationally highly excited products,and the retention of configuration more relevant due to a much morestable halogen-bonded prereaction complex supporting front-side attack,with respect to the Cl^–-leaving-group process. Severalfurther retention mechanisms of the title reaction are identified,as well, interestingly excluding multi-inversion, recently discoveredat the nitrogen-center, while inversion mainly occurs through stripping.The proton-transfer channel, favoring also the stripping mechanism,is a primarily direct process with less internal excitation in theproducts, similarly distributed between rotation and vibration.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"561–570"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical Oxidation of Coronene: A Crystallographic and Computational Study of Charge-Regulated π-Stacking","authors":"Rameswar Bhattacharjee,&nbsp;Megan E. McCormack,&nbsp;Yikun Zhu,&nbsp;Zheng Wei,&nbsp;Miklos Kertesz,&nbsp;Marina A. Petrukhina","doi":"10.1021/acsphyschemau.6c00020","DOIUrl":"10.1021/acsphyschemau.6c00020","url":null,"abstract":"<p>Chemical oxidation of coronene with [Et₃O⁺SbCl₆^–] in dichloromethane allowedtheisolation and crystallization of a dimeric coronene radical cationin the form of [(C₂₄H₁₂)₂^•+(SbCl₆^–)][Et₃O⁺SbCl₆^–]₂, as revealed crystallographically.The crystal structure exhibits π-stacked columns of coronenemolecules, wherein alternating average interplanar contacts of 3.357(2)and 3.452(2) Å show the distinct formation of the coronene dimers.This packing is accompanied by an atom-over-atom overlap motif andcore deformation often associated with a unique intermolecular interactioncalled pancake bonding. A combined computational analysis employingfinite cluster and periodic density functional theory (DFT) calculationsconfirms the presence of pancake bonding and delineates its hierarchicalstrength along the column. Charge-distribution analyses identify themolecular oxidation states and demonstrate that Coulombic repulsionbetween charged dimers plays a decisive role in enforcing the observedalternation of interplanar distances. Periodic DFT modeling of aninfinite coronene stack faithfully reproduces the experimental structuralparameters and provides insight into the electronic structure of theresulting one-dimensional π-radical assembly.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"571–579"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cation-Surface Interactions During Electrocatalytic Hydrogen Evolution Probed by Surface X-ray Diffraction","authors":"Mariana C. O. Monteiro,&nbsp;Leon Jacobse,&nbsp;Arthur M. V. Hagopian,&nbsp;Vedran Vonk,&nbsp;Simon Chung,&nbsp;Sheena Louisia,&nbsp;Alexander Meinhardt,&nbsp;Elif Öykü Alagöz,&nbsp;Xin Deng,&nbsp;Beatriz Roldan Cuenya,&nbsp;Katharina Doblhoff-Dier,&nbsp;Marc T. M. Koper,&nbsp;Andreas Stierle","doi":"10.1021/acsphyschemau.5c00152","DOIUrl":"10.1021/acsphyschemau.5c00152","url":null,"abstract":"<p>The electrocatalytic production of hydrogen is pivotalfor thesustainable generation of hydrogen fuel and hydrogen as reducing agent.Metal cations in alkaline electrolytes can facilitate or significantlyimpede this reaction, depending on electrolyte pH, catalyst surface,cation identity, and concentration. Still, the underlying mechanismsgoverning these effects remain elusive, in part due to the lack ofdirect characterization of how cations interact with the electrocatalystsurface and interfacial water. Here, using Surface X-ray Diffractioncombined with ab initio Molecular Dynamics, we elucidate the formationof a cation layer at the electrochemical interface during hydrogenevolution on a hexagonally reconstructed Au(100) model catalyst undervarying pH, potential, cation concentration, and electrolyte composition.Specular Crystal Truncation Rod measurements show that as the potentialbecomes more negative, Cs⁺ cations increase in surfacecoverage and move progressively closer to the interface, revealingthat the positions of the inner- and outer-Helmholtz planes continuouslyshift with potential. Slightly smaller cation-to-surface distancesand higher coverages are observed in alkaline media compared to acidicenvironments. Ab initio Molecular Dynamics simulations reveal thatthe Cs⁺ ions move into the first water layer as they approachthe surface at more negative potentials. No water molecules can thenreside between the ions and the Au surface, leading to a broken solvationsymmetry and an opening angle. This opening is initially establishedby an orientation and slight distortion of the solvation shell, whileat shorter ion-surface distances the ion sheds ∼10% of itssolvation, enabling a closer approach to the surface. Finally, inLi⁺/Cs⁺ electrolyte mixtures at pH 3, we observethe preferential accumulation of Cs⁺ at the electrochemicalinterface, albeit in a more disordered fashion compared to the Li⁺-free situation. This is expected to enhance interfacial mobilityand influence electrocatalytic activity beyond traditional “structuremaking/breaking” descriptions.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"503–513"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Tutorial on Mechanistic Modeling of Nonstatistical Reactivity: Example of Light and Heat Effects in the Garratt–Braverman/[1,5]-H Shift of Ene-diallenes","authors":"Tomislav Rožić,&nbsp;Yuxuan Hou,&nbsp;Lea K. Northcote,&nbsp;Christian Marcus Pedersen,&nbsp;Gemma C. Solomon","doi":"10.1021/acsphyschemau.6c00003","DOIUrl":"10.1021/acsphyschemau.6c00003","url":null,"abstract":"<p>Broad terms in the literature, such as nonstatisticalreactivityor nontraditional luminescence, emerge when standard theories failto explain experimental results. In the case of nonstatistical anddynamic effects, reaction rates and product ratios may vary wildlyfrom transition state theory (TST) predictions and are commonly accompaniedby a lack of temperature dependence. In this Tutorial, we explainhow to use modern and freely available computational chemistry toolsto model apparently nonstatistical reactions in relatively large organicmolecules, using a concrete example of the thermal Garratt–Braverman/[1,5]-Hshift of an ene-diallene, such that a non-expert can easily replicateour approach by following our steps. As a team of synthetic organicchemists and computational chemists, we aim to promote the use ofpreparatory computational work that can aid in reaction design duringthe experimental process rather than merely serving as complementarydata to finished experimental studies. For this reason, we also offeran overview of the literature leading into more advanced computationaltechniques. Working through the example of the thermal Garratt–Braverman/[1,5]-Hshift, we illustrate how theory and experiment can be used togetherto investigate the possibility of parallel light-enabled reactionsand the role of tunneling effects and to perform careful variabletemperature analysis when it becomes necessary. As the motifs of reactiveπ–π* absorptions, hydrogen transfers, and diradicalintermediates are quite common, the points presented in this Tutorialare broadly applicable and indicative of the underlying complexitybehind many chemical reactions that exhibit unexpected rates and ratios.The failure of TST also underscores a critical limitation of massivereaction network discovery schemes that heavily rely on calculatedground-state activation energies as well as the potential pitfallsof the conventional free energy diagram mindset.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"393–407"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chirality Transfer in Gold Nanoclusters: Insights from Chiral Spectroscopy and Theoretical Modeling","authors":"Rareş Banu,&nbsp;Chiara Morassut,&nbsp;Ariel Perez Mellor,&nbsp;Thomas Bürgi,&nbsp;Mauro Stener,&nbsp;Noelia Barrabés","doi":"10.1021/acsphyschemau.6c00014","DOIUrl":"10.1021/acsphyschemau.6c00014","url":null,"abstract":"<p>Chirality in atomically precise gold nanoclusters emergesfromthe interplay among the metal core, the metal–ligand interface,and the ligand shell, yet how these hierarchical elements influenceligand conformation remains unclear. This work investigates chiralitytransfer from the nanocluster framework to the ligand sphere by usingvibrational circular dichroism (VCD) spectroscopy combined with densityfunctional theory and SCC-DFTB calculations. Three enantiopure thiolate-protectedgold nanoclusters─Au₂₅(2-MeBuS)₁₈, Au₃₈(2-MeBuS)₂₄, and Au₁₄₄(2-MeBuS)₆₀─were selected as model systems, representing one,two, and three hierarchical levels of chirality, respectively. VCDanalysis reveals a progressive restriction and reorganization of theligand conformations with increasing structural chirality. While theintrinsically achiral Au₂₅ induces only modest spectralchanges, the chiral arrangement of the staple units in the Au₃₈ induces significant changes in both IR and VCD spectra.In Au₁₄₄, the additional chiral gold core leads to a strongamplification of the VCD response. Computational analysis shows thatligand conformations are governed by cluster geometry, with bindingfavoring the most stable free ligand conformer. These results providedirect insight into chirality transfer mechanisms in gold nanoclusters,leading to a better understanding of the design of chiral nanomaterials.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"552–560"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Seasons of a Career in Physical Chemistry: Olivia Harper Wilkins","authors":"Olivia H. Wilkins,&nbsp;Joan-Emma Shea,&nbsp;Gregory D. Scholes,&nbsp;Gemma C. Solomon","doi":"10.1021/acsphyschemau.6c00079","DOIUrl":"10.1021/acsphyschemau.6c00079","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 3","pages":"389–392"},"PeriodicalIF":4.8,"publicationDate":"2026-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148139129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}