The Journal of Physical Chemistry A最新文献

{"title":"Quantitative Modeling of Excited-State Dynamics in Valence Photoionized Vinyl Fluoride.","authors":"Luka Dockx, Bálint Sztáray, Anthony D Dutoi","doi":"10.1021/acs.jpca.5c03431","DOIUrl":"10.1021/acs.jpca.5c03431","url":null,"abstract":"<p><p>Long-standing debates regarding the dissociative photoionization of vinyl fluoride (fluoroethene) were resolved using large-scale surface-hopping ab initio molecular dynamics (SH-AIMD) simulations. By combining accurate initial condition sampling, electronic cross-section calculations, and SH-AIMD with density functional theory (DFT) and complete active space second-order perturbation theory (CASPT2), we obtained not only qualitative insight into excited-state dynamics but also quantitatively accurate predictions of the photoelectron spectrum, fluorine-loss branching ratios, and translational kinetic energy release distributions for F + C₂H₃⁺ products. Statistical dissociation arises from the <b>X̃</b> ²A″-<b>B̃</b> ²A' states, while, in the <b>C̃</b> ²A″-<b>Ẽ</b> ²A' states, excited-state dissociation within 50-250 fs dominates. Only CASPT2 captures the formation of an excited triplet C₂H₃⁺ fragment, though DFT still reproduces correct branching ratios, as branching pathways are largely determined at short bond distances. Importantly, the previously hypothesized inclusion of autoionizing Rydberg states is not required to match experimental observables.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6632-6637"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635769","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":"Real Space Partitioning of the First Hyperpolarizability.","authors":"Ismael Vargas-Rodríguez, Juvencio Robles, Tomás Rocha-Rinza, Adán Bazán-Jiménez, Itzel Mercado-Sánchez, Rogelio Chávez-Rocha, Evelio Francisco Miguelez, Ángel Martín Pendás, Marco A García-Revilla","doi":"10.1021/acs.jpca.5c01791","DOIUrl":"10.1021/acs.jpca.5c01791","url":null,"abstract":"<p><p>Two approximate partitioning schemes for the principal component of the first static hyperpolarizability are introduced within the framework of the quantum theory of atoms in molecules (QTAIM). The first approach employs a two-state model, while the second utilizes finite difference techniques. Both methods decompose the principal hyperpolarizability component into contributions arising from atom polarizations and charge transfer. We decompose the hyperpolarizability of 14 D-π-A systems. Our results highlight the dominant role of the charge transfer component. Moreover, a strong correlation is observed between the strength of the donor and acceptor groups and the activation of the π-fragment, which amplifies the principal hyperpolarizability component. Notably, the acceptor fragments across different compounds exhibit partially transferable hyperpolarizability values. These findings shed light on the intricate relationship between functional group characteristics and the nonlinear optical properties of molecules, offering strategic insights into the rational design of advanced materials tailored for optical applications.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6562-6571"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635770","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":"","authors":"Fatima H. Garcia,&nbsp;Jennifer L. Pore*,&nbsp;Jacklyn M. Gates,&nbsp;Heather L. Crawford,&nbsp;Alexander Ditter,&nbsp;Paul Fallon,&nbsp;John K. Gibson,&nbsp;John Gooding,&nbsp;Mallory McCarthy,&nbsp;Rodney Orford,&nbsp;Ziad Shafi,&nbsp;David K. Shuh and Mark A. Stoyer,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 29","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c02098","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting the H₅O₂⁺ IR Spectrum with VSCF/VCI and the Influence of Mark Johnson's Experiments in Advancing the Theory of Protonated Water Clusters.","authors":"Ruitao Ma, Chen Qu, Paul L Houston, Riccardo Conte, Apurba Nandi, Joel M Bowman, Qi Yu","doi":"10.1021/acs.jpca.5c03748","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03748","url":null,"abstract":"<p><p>The interplay between experiment and theory is widely appreciated in the fields of chemical physics and physical chemistry. Indeed, some experiments actually push the frontiers of theory. This is the case for protonated water clusters and, in particular, the experiments of the Mark Johnson group on the Zundel and Eigen cations, H₅O₂⁺ and H₉O₄⁺, respectively, and the challenging \"in-between\" cation H₇O₃⁺. In this perspective, we demonstrate this with a focus on H₅O₂⁺ and, specifically, the strong doublet feature of the proton stretch, uncovered experimentally by Johnson's group. This proved to be a major challenge for theory, from developing \"gold standard\" potential energy surfaces to quantum dynamics. Full-dimensional multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) calculations using an accurate potential and dipole moment surface were the first quantum ones to capture this feature, as well as the full IR spectrum. Earlier vibrational self-consistent field and virtual state configuration interaction (VSCF/VCI) calculations, using the code MULTIMODE, were unable to describe this owing to a lack of convergence. We show here that pushing that approach does recover the doublet and overall an IR spectrum, in agreement with the earlier MCTDH and recent time-dependent tree tensor network states (td-TTNS) and experiment. VSCF/VCI and subsequent very computationally intensive ML-MCTDH calculations of the IR spectrum of the Eigen isomer of H₉O₄⁺ produce very good agreement with Johnson's experimental one. These calculations were performed with an ab initio many-body potential and dipole moment surface. The VSCF/VCI MULTIMODE approach has been extended to the larger clusters, and this is shown for two isomers of H₁₃O₆⁺, with very good agreement with experimental spectra.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144705804","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":"Tetrahedral Mg₃M Clusters: A New Class of Superatom Catalysts for the Suzuki-Miyaura Reaction.","authors":"Wen-Lu Wang, Zhi-Chao Zhang, Wei-Huang Wang, Bi-Lian Ni, Wei-Ming Sun","doi":"10.1021/acs.jpca.5c02579","DOIUrl":"10.1021/acs.jpca.5c02579","url":null,"abstract":"<p><p>Exploring low-cost and high-activity cluster catalysts for the Suzuki-Miyaura (SM) reaction based on the intriguing superatom concept is of great interest. To achieve this goal, a series of Mg₃M (<i>M</i> = Sc-Zn) clusters have been obtained via the rational design and random search in this study. The superatom identities of these Mg₃M clusters are guaranteed by their compact tetrahedral structures, high stability, and superatomic configurations. The performance of these Mg₃M superatoms in adsorbing benzene halides as well as catalyzing the oxidative addition, transmetalation, and reductive elimination steps of the SM reaction was evaluated step by step to screen out feasible catalysts for the SM reaction. Finally, Mg₃Ni was selected as the best superatom catalyst for the SM reaction among these Mg₃M superatoms in view of its low rate-limiting energy barrier of 24.94 kcal/mol, which is even lower than that of 26.35 kcal/mol for Mg₃Pd. Moreover, the catalytic performance of Mg₃Ni deposited on a graphitic carbon nitride (g-C₃N₄) in the rate-limiting step of the SM reaction was assessed to confirm the practical application of this superatom in the catalysis of the SM reaction. This study not only provides cheap replacement catalysts of noble metals for SM reaction, but also intrigues researchers' interests to further extend the practical application of superatom clusters in catalyzing other C-C coupling reactions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6581-6592"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606793","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":"Stereodynamical Control on the Br (²P_3/2, ²P_1/2) + H₂ (<i>v</i> = 0, <i>j</i> = 1) → HBr + H Reactions.","authors":"Xiaoxi Xu, Bayaer Buren, Maodu Chen","doi":"10.1021/acs.jpca.5c02235","DOIUrl":"10.1021/acs.jpca.5c02235","url":null,"abstract":"<p><p>The stereodynamical control of collision partners can profoundly influence the reactive scattering result. This study investigates the stereodynamical control of the Br (²P_3/2, ²P_1/2) + H₂ (<i>v</i> = 0, <i>j</i> = 1) → HBr + H reactions using the time-dependent wave packet method, by manipulating the alignment angle β between the bond axis (described by both the azimuth angle α and polar angle β) of the rotationally excited H₂ molecule and the relative velocity of the collision partners. A two-state model is used for the calculations. Analysis of the integral scattering cross sections reveals that both β = 0° and β = 90° configurations enhance reactivity, whereas β = 30, 45, and 60° configurations show inhibitory effects. Differential cross sections show that the β = 90° configuration enhances the sideways scattering of both reactions, while the β = 0° configuration is more preferred for inducing backward scattering. The analysis reveals that backward scattering products can be obtained in the excited spin-orbit state reaction by head-on collisions in the low collision energy region, and sideways scattering products can be obtained in the high collision energy region by side-on collisions. In contrast, the direction of scattering is more easily controlled at the high collision energy region in the ground spin-orbit state reaction. In the present work, we also further reveal the crucial role of interferences in the stereodynamical control of the reactions when the differential cross sections are observed.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6572-6580"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635771","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":"Photoinduced Intramolecular [2 + 2] Cycloaddition Investigated with Transient Infrared Spectroscopy.","authors":"Valerie S Winkler, Caroline G Cramer, Joseph A Fournier","doi":"10.1021/acs.jpca.5c02822","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02822","url":null,"abstract":"<p><p>The use of visible light to drive chemical reactions has become an increasingly popular synthetic approach in organic and polymer chemistries. However, photodriven reaction dynamics and mechanisms remain difficult to elucidate. Here, we report the dynamics and kinetics of a photoinitiated intramolecular [2 + 2] cycloaddition reaction using ultrafast transient infrared spectroscopy spanning 100 fs to 1 ns after photoexcitation. Vibrational signatures of the product species, consisting of a bicyclo[3.2.0]heptane-2,4-dione core, appear within ∼300 ps following visible excitation at 430 nm. We performed global fitting analysis to a four-step sequential reaction model. The resulting kinetics are hypothesized to derive from fast vibrational relaxation within the initially excited S₃ electronic state (∼160 fs), followed by internal conversion (∼3 ps). A key intermediate state or species then forms on a ∼30 ps time scale, which is postulated to arise from intersystem crossing to the triplet manifold. The final step is the rate-limiting transformation to the product occurring with a ∼260 ps time constant.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697120","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":"","authors":"Ismael Vargas-Rodríguez,&nbsp;Juvencio Robles,&nbsp;Tomás Rocha-Rinza,&nbsp;Adán Bazán-Jiménez,&nbsp;Itzel Mercado-Sánchez,&nbsp;Rogelio Chávez-Rocha,&nbsp;Evelio Francisco Miguelez,&nbsp;Ángel Martín Pendás* and Marco A. García-Revilla*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 29","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c01791","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Peter H. Dinolfo*,&nbsp;Tyler J. Mucci,&nbsp;Adrian J. Riives,&nbsp;Jeremy R. Brinker and William D. Arthur,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 29","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c03562","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solvent Dependence of [Au₁₁(BINAP)₄X₂: X = Cl or Br]⁺ Cluster Electronic and Optical Properties.","authors":"Daniel J Heintzelman, Jane A Knappenberger, Kenneth L Knappenberger","doi":"10.1021/acs.jpca.5c03523","DOIUrl":"10.1021/acs.jpca.5c03523","url":null,"abstract":"<p><p>Complex cluster-solvent interactions were investigated for 11-metal-atom monolayer-protected gold nanoclusters dispersed in a variety of solvents. Ultraviolet-visible (UV-vis), photoluminescence, and femtosecond transient absorption (fs-TA) spectroscopies were employed to examine the effect of solvent identity on the photophysical properties of [Au₁₁(BINAP)₄X₂]⁺, where X represents Cl or Br. UV-vis absorption spectra showed a narrowing of spectral peaks when the clusters were dispersed in protic solvents, indicating increased cluster rigidity in these solvents. Photoluminescence studies revealed that emission profiles can be tuned by modulating the cluster-solvent interaction. fs-TA experiments further supported the assignment of distinct radiative decay pathways based on the strength of the cluster-solvent interactions and also demonstrated that ethanol binding to [Au₁₁(BINAP)₄X₂]⁺ clusters is more thermodynamically stable than butanol binding. ¹H nuclear magnetic resonance spectroscopy provided evidence for cluster-solvent hydrogen bonding between [Au₁₁(BINAP)₄Cl₂]⁺ and ethanol in the form of downfield-shifted and exchange-broadened peaks. These data indicate that cluster-solvent hydrogen bonds can be tuned, emphasizing the important role of the solvation shell in determining the electronic and optical properties of atomically precise nanoclusters.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6638-6643"},"PeriodicalIF":2.7,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606792","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}