The Journal of Physical Chemistry A最新文献

{"title":"Effective Mass Accommodation Model for Surface and Bulk Reactions in Particles","authors":"Pascale S. J. Lakey,&nbsp;Manabu Shiraiwa","doi":"10.1021/acs.jpca.6c02721","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c02721","url":null,"abstract":"<p>Mass accommodation is a criticalprocess, controllinguptake coefficientsof gaseous species in aerosols and clouds. The effective mass accommodationcoefficient (α_eff) was developed to account for kineticlimitations of bulk diffusion and reactions with a simple analyticalequation. In this work, α_eff is extended by includingsurface reactions and bulk accommodation. Systematic simulations overa wide range of kinetic parameters demonstrate excellent agreementbetween the α_eff method and a benchmark kinetic multilayermodel once quasi-equilibrium is achieved in the effective penetrationdepth. The α_eff method can quantify the contributionsof surface and bulk processes to overall uptake. Comparisons withtwo other models (Wilson et al., 2022; Prophet and Wilson, 2025) showthat the α_eff method more accurately predicts uptakecoefficients when uptake is limited by bulk diffusion of volatilespecies or when surface reactions dominate under high surface coverageconditions. The developed method provides a useful tool for analyzingexperimental measurements and developing uptake parametrizations forlarge-scale models.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7197–7210"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Elucidating Protomer Structures and Fragmentation Dynamics of Protonated Aminobenzoic and Aminocinnamic Acids via Cryo-Ion Mobility and Laser Spectroscopy","authors":"Yoshiya Inokuchi,&nbsp;Kengo Tsunoda,&nbsp;Amiru Ohata,&nbsp;Motoki Kida,&nbsp;Satoru Muramatsu,&nbsp;Keigo Hattori,&nbsp;Daiki Fuse,&nbsp;Keijiro Ohshimo,&nbsp;Fuminori Misaizu","doi":"10.1021/acs.jpca.6c04038","DOIUrl":"10.1021/acs.jpca.6c04038","url":null,"abstract":"<p>Biological and synthetic systems featuring coexistingamino andcarboxy groups, such as amino acids and peptides, serve as vital modelsfor understanding hydrogen-bonded proton transport networks. Unambiguouslyidentifying protonation isomers (protomers) is crucial yet challenging,as their structures are heavily modulated by both intrinsic stabilitiesand extrinsic solvent environments. Here, we present a comprehensiveinvestigation into the protonation sites and geometric structuresof protonated 4-aminobenzoic acid (H⁺(4ABA)) and 4-aminocinnamicacid (H⁺(4ACA)) utilizing a synergistic combination ofcryogenic ion mobility-mass spectrometry (Cryo-IM-MS), UV photodissociation(UVPD) and IR-UV double-resonance (IR-UV DR) spectroscopy, and quantumchemical calculations. Cryo-IM-MS demonstrates a pronounced solvent-dependentprotomer distribution, where electrospray ionization from H₂O/CH₃OH = 1:1 and CH₃CN solution predominantlyyields the O- and N-protomers, respectively. Isomer-selective IR-UVDR spectroscopy successfully pins down the precise spatial orientationsof the functional groups. Crucially, H⁺(4ABA) and H⁺(4ACA) exhibit markedly distinct photofragmentation pathwaysdriven by the unsaturated alkenyl link in H⁺(4ACA). Whilethe H⁺(4ABA) O-protomer undergoes competitive decarboxylation(CO₂ loss) and dehydration (H₂O loss), the extendedπ-conjugation in H⁺(4ACA) introduces a substantialkinetic bottleneck that completely suppresses CO₂ elimination.In the case of the H⁺(4ACA) N-protomer, the alkenyl groupacts as an active, structurally preorganized hydrogen source, facilitatinghighly efficient H₂O loss via a tightly constrained transitionstate. These results provide profound fundamental insights into howstructural modifications and local environments dictate competitivedeactivation pathways, offering broader implications for the designand understanding of functional charge-transport materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7141–7152"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148917591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Photochemistry of the Stilbenes in Methanol. Trapping the Common Phantom Singlet State”","authors":"Jack Saltiel,&nbsp;Shipra Gupta","doi":"10.1021/acs.jpca.6c05061","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05061","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7265–7266"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bridging Electron Density Relaxation and XPS Spectroscopy: Orbital-Resolved Trends in Core-Ionized Aum (m = 4, 10, 20) and (TiO2)n (n = 2–4) Clusters","authors":"Bartłomiej Gostyński","doi":"10.1021/acs.jpca.6c01107","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c01107","url":null,"abstract":"<p>Core electron binding energies (CEBEs) in nanomaterialsencodeelement-specific chemical information, yet their interpretation isoften complicated by quantum size effects and site-to-site heterogeneityin small finite systems. Here, I use all-electron Δ-Self ConsistentField (ΔSCF) density functional theory to quantify site-resolvedCEBEs and the accompanying orbital-level relaxation response in twochemically distinct cluster families: metallic Au_<em>m</em> (<em>m</em> = 4, 10, 20) and anatase-like (TiO₂)_<em>n</em> (<em>n</em> = 2–4),including multiple structural isomers. Beyond total-energy differences,I analyze the orbital-resolved Kohn–Sham eigenvalue shift,Δε, induced by a localized core–hole. Finally,I assess a summed eigenvalue-shift descriptor, ΣΔε,as a compact reduction of these data. The results highlight the intrinsicallyquantum-mechanical origin of core-level shifts in finite systems andsuggest that orbital-resolved relaxation patterns may serve as auxiliary,physically interpretable descriptors in future core-level spectroscopystudies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7071–7085"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Model to Derive Langmuir–Hinshelwood Parameters from Heterogeneous Uptake Experiments in a Fast Flow Reactor","authors":"Egor V. Demidov,&nbsp;Alexei F. Khalizov","doi":"10.1021/acs.jpca.6c03212","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c03212","url":null,"abstract":"<p>Heterogeneous interactionsbetween reactive trace gases and aerosolparticles alter both the atmospheric trace gas composition and thechemical properties of the participating particles. Incorporatingthese interactions into aerosol models requires kinetic parameters,which are often derived from uptake experiments in flow reactors andare typically limited to uptake coefficients. We present a frameworkthat enables the extraction of a more fundamental set of kinetic parameters,including adsorption, desorption, and reaction rate constants, aswell as the concentrations of adsorptive and reactive sites, directlyfrom such uptake data. The framework is currently formulated for theLangmuir–Hinshelwood mechanism on a solid surface but can bereadily extended to other mechanisms. The model for time-dependentgas-phase mass transfer and surface chemistry that this frameworkis based on was developed procedurally, starting from the most rigorousimplementation and undergoing two major simplifications, enablingcomputationally efficient fitting to experimental data. Applicationof the framework was demonstrated by fitting the model to experimentaluptake curves, deriving uptake coefficients and partitioning constantsfrom fitted parameters at both experimental and atmospheric conditions.Finally, an analytical approach for predicting partitioning throughreactive Langmuir–Hinshelwood uptake was derived that can improvethe accuracy of treating partitioning in aerosol models at no additionalcomputational cost.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7232–7252"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactivity of Nb3N3–xOx+ (x = 0–3) toward Methane: Ligand-Controlled Modulation of Nb–Nb σ Bonds","authors":"Xiao-Xiao Liu,&nbsp;Xi-Guan Zhao,&nbsp;Yu-Zhe Hu,&nbsp;Zi-Yu Li,&nbsp;Sheng-Gui He","doi":"10.1021/acs.jpca.6c04728","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04728","url":null,"abstract":"<p>Mildactivation of methane remains a fundamental challengedueto its chemical inertness. While metal–metal σ-bond-mediatedpathways have recently emerged as an effective strategy, how mixedligands regulate reactivity of dual-metal centers remains poorly understood.Herein, we investigate the reactivity of Nb₃N_{3–<em>x</em>}O_<em>x</em>⁺ (<em>x</em> = 0–3) clusters toward CH₄ using time-of-flightmass spectrometry combined with theoretical calculations. A clearevolution of reactivity is observed upon stepwise substitution ofN with O, with reaction channels shifting from exclusive adsorption(Nb₃N₃⁺) to concurrent adsorptionand dehydrogenation (Nb₃N₂O⁺, Nb₃NO₂⁺), and ultimately to efficient dehydrogenation(Nb₃O₃⁺). Mechanistic analysis revealsthat methane activation occurs at Nb–Nb dual-metal centers,whose reactivity is governed by ligand-controlled number and distributionof Nb–Nb σ bonds. Nitrogen ligands disrupt σ bondingand reduce active sites, whereas oxygen ligands preserve intact dinuclearmotifs and promote synergistic C–H activation. These findingsclarify how ligand coordination controls metal–metal bondingand governs dual-metal site reactivity, providing molecular-levelinsights into methane activation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7177–7186"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intermolecular Interactions of Large Systems: Boron Nitrides, Acenes, and Coronenes","authors":"Vladimir Fishman,&nbsp;Jan M. L. Martin,&nbsp;A. Daniel Boese","doi":"10.1021/acs.jpca.6c01896","DOIUrl":"10.1021/acs.jpca.6c01896","url":null,"abstract":"<p>In a recent contribution [Fishman et al., <em>J. Chem. Theory Comput.</em> <strong>2025</strong>, 21, 2311–2324], we introducedanother approach to benchmarking noncovalent interactions by not benchmarkinginteraction energies of different dimers but by considering the evolutionof interaction energies with increasing system size. Here, we extendthe benchmark set to more species, such as electrostatically boundborazine dimers as well as the minimum-energy structures of paralleldisplaced acene and coronene dimers. While the minimum structuresof the parallel displaced acene dimers yield similar results to previouslypublished sandwich-structured acenes, the borazine dimers behave vastlydifferently, yielding a yet more complete picture of noncovalent interactionsand their scalability. In contrast, the polycyclic aromatic hydrocarbonstructures─coronenes sandwich-stacked and coronenes paralleldisplaced─give results consistent with those obtained for bothtypes of the polyacene series, resulting in an updated estimate forthe coronene dimer energy. By doing so, we are able to break downvarious approximations made by state-of-the-art coupled-cluster methods.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7086–7098"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148917738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density Functional Analysis of Noncovalent 2- and 3-Body Interactions in Trimolecular Clusters","authors":"Davide Massafra,&nbsp;Hanwei Li,&nbsp;Eric Brémond,&nbsp;Juan Carlos Sancho-García,&nbsp;Orlando Crescenzi,&nbsp;Frédéric Labat,&nbsp;Carlo Adamo","doi":"10.1021/acs.jpca.6c02847","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c02847","url":null,"abstract":"<p>The performance of several densityfunctionals for thedescriptionof 3-body interactions was evaluated on three benchmark data sets:3B-69, S22(3), and 3BHET. Only a few DFT methods achieve consistentaccuracy, notably B97-based functionals (ωB97X-V, ωB97X-D,and B97M-V) and double hybrids such as PBE-QIDH-D3(BJ) and B2-PLYP-D3(BJ).If dispersion corrections are essential for describing 2-body interactions,accurate 3-body energies require the presence of a significant fractionof Hartree–Fock exchange. Among dispersion models, those castinginformation from the electron density, like VV10, XDM, and MBD, providethe best performance. These last models also provide a qualitativeagreement with the classical Axilrod–Teller–Muto modelfor trimers in the S22(3) data set, an indication that they providea reasonable description of the long-range dispersion component ofthe 3-body interactions. Overall, these data sets remain more challengingthan standard noncovalent benchmarks due to the subtle electroniceffects governing many-body interactions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7217–7231"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conical Intersection-Mediated Nonradiative Decay in an ESIPT-Active Imidazole Derivative","authors":"Jiahui Wu,&nbsp;Chuanbiao Zhang,&nbsp;Dan Wang,&nbsp;Zhiyuan He","doi":"10.1021/acs.jpca.6c05123","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05123","url":null,"abstract":"<p>Excited-state intramolecular protontransfer (ESIPT) is a photoinducedprocess that involves proton migration within an intramolecular hydrogen-bondedframework following electronic excitation and is often associatedwith large Stokes-shifted emission. However, the excited-state fateafter proton transfer is not exclusively governed by radiative decayfrom a stabilized keto tautomer, and nonradiative relaxation may alsoplay a decisive role. In this work, the excited-state relaxation mechanismof 2-(4,5-diphenyl-1<em>H</em>-imidazol-2-yl)phenol (DIP)was investigated using multireference electronic structure calculationscombined with nonadiabatic dynamics simulations. SA-CASSCF/MS-CASPT2calculations reveal the presence of a low-energy S₁S₀ conical intersection in the keto configuration that providesan efficient nonradiative decay channel. The ESIPT process proceedsthrough a modest proton-transfer barrier of 7.47 kcal·mol⁻¹, after which the system is directed toward the conicalintersection region on the excited-state potential energy surface.Surface-hopping dynamics simulations at the OM2/MRCI level furtherdemonstrate that the relaxation process bifurcates into pathways yieldingeither enol or keto ground-state products. These results indicatethat the excited-state dynamics are governed not only by proton transferbut also by strong nonadiabatic coupling associated with the conicalintersection. This work reveals that the excited-state fate of ESIPTsystems is strongly governed by conical intersection-mediated nonradiativedecay following proton transfer.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7187–7196"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Energy-Dependent Evolution of Novel Relativistic Quantum Many-Body Hidden Satellites in Zinc X-Ray Emission Revealed by XR-HERFD","authors":"Ramesh Rijal,&nbsp;Pierce Bowman,&nbsp;Daniel Sier,&nbsp;Minh H Dao,&nbsp;Chanh Q Tran,&nbsp;Shusaku Hayama,&nbsp;Matteo Aramini,&nbsp;Nitya Ramanan,&nbsp;Sofia Diaz-Moreno,&nbsp;Christopher T Chantler","doi":"10.1021/acs.jpca.6c04572","DOIUrl":"10.1021/acs.jpca.6c04572","url":null,"abstract":"<p>We present the first experimental observation of long-unresolvedmany-body satellite features within the Kα_1,2 X-rayemission spectra of zinc (Zn) with statistical significance exceeding50 σ_<em>se</em> per data point. These novelstructures, “Hidden Satellites”, were discovered usingan extended-range high-energy-resolution fluorescence detection (XR-HERFD)technique at the I20-Scanning beamline of the Diamond Light Sourcein UK. The measurements employed a 14-crystal analyzer array specificallydesigned to enhance both energy resolution and statistical accuracy.The Hidden Satellites are revealed within the main Kα_1,2 emission peak and exhibit a systematic evolution with increasingincident photon energy. Principal component analysis (PCA) was employedto independently isolate these novel features and trace the evolutionof these structures. Remarkably, these hidden features contribute15% to 20% of the total emission intensity, directly challenging thelong-standing assumption that the many-body reduction factor (<span><em>S</em><span>²₀</span></span>) is constant. We observe that <span><em>S</em><span>²₀</span></span> exhibits a clear energy dependence,changing by over 20% over the observed energy range, with broad implicationsfor the analysis and interpretation of X-ray absorption and emissionspectra in transition metals and their compounds. Overall, it providesa new foundation for interpreting X-ray spectroscopy, influencingthousands of studies across chemistry, physics, and biology. Despitezinc metal being considered a “simple” d¹⁰ metal, the complexity of structure, asymmetry and evolution of thesenew processes is dramatic and points to a rich new area of inquiry.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 36","pages":"7253–7264"},"PeriodicalIF":3.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148917652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}