The Journal of Physical Chemistry A最新文献_第5页

A Tetrameric Cobalt(II) Assembly Integrating Aggregation-Induced Emission and Weak Antiferromagnetic Coupling 一种集聚集诱导发射和弱反铁磁耦合于一体的四聚体钴（II）组装体

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-01 Epub Date: 2026-09-19 DOI: 10.1021/acs.jpca.6c05412

Sharsti Goyal, Sakshi Mehta, Shashank Kumar Mishra, Abhineet Verma

{"title":"A Tetrameric Cobalt(II) Assembly Integrating Aggregation-Induced Emission and Weak Antiferromagnetic Coupling","authors":"Sharsti Goyal, Sakshi Mehta, Shashank Kumar Mishra, Abhineet Verma","doi":"10.1021/acs.jpca.6c05412","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05412","url":null,"abstract":"A supramolecularly rigidified tetrameric cobalt(II) assembly,[Co4T8(H2O)2] (T-Co), where T = Tropolonateion, has been constructed using tropolonate ligands to investigatethe interplay between aggregation-controlled photophysics and magneticexchange interactions in multinuclear 3d systems. Single-crystal analysisreveals a distorted octahedral Co4 framework interconnectedthrough oxygen-bridged pathways and reinforced by cooperative O–H···Ohydrogen bonding, π–π stacking, and C–H···πinteractions, producing an extended caterpillar-like supramoleculararrangement. The restricted structural dynamics imposed by this denselypacked architecture give rise to pronounced aggregation-induced emission(AIE) behavior, in which progressive aggregation in water-rich mediaenhances fluorescence by suppressing nonradiative relaxation channels.Dynamic light scattering measurements correlate the emissive enhancementwith aggregate growth, confirming aggregation-governed excited-statemodulation. Magnetic studies reveal weak antiferromagnetic exchangebetween high-spin Co(II) centers, accompanied by pronounced single-ionmagnetic anisotropy arising from spin–orbit coupling and rapidmagnetization dynamics, although slow magnetic relaxation characteristicof robust single-molecule magnets is not observed. The present studydemonstrates how supramolecular organization within a polynuclearcobalt framework simultaneously dictates excited-state confinementand magnetic communication, providing a viable strategy for engineeringmultifunctional luminescent magnetic materials through cooperativestructural rigidification.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 39","pages":"7844–7851"},"PeriodicalIF":3.0,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093633","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}

引用次数: 0

Rovibrational-Specific Kinetics Database and Master Equation Study for the O2 + N and NO+O Systems Using Ground Electronic State NO2 Potential Energy Surfaces 基于基态NO2势能面O2 + N和NO+O体系的振动动力学数据库和主方程研究

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-01 Epub Date: 2026-09-16 DOI: 10.1021/acs.jpca.6c02327

Luis F. Rodriguez, Robyn L. Macdonald

{"title":"Rovibrational-Specific Kinetics Database and Master Equation Study for the O2 + N and NO+O Systems Using Ground Electronic State NO2 Potential Energy Surfaces","authors":"Luis F. Rodriguez, Robyn L. Macdonald","doi":"10.1021/acs.jpca.6c02327","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c02327","url":null,"abstract":"Motivated by the study of high-enthalpy air flows, thiswork investigatesthe nonequilibrium kinetics of the O2 + N and NO + O systems.Rovibrationally resolved kinetic data for the O2 + N andNO + O systems are generated using quasi-classical trajectory (QCT)simulations performed on high-fidelity ab initio potential energysurfaces (PESs). State-specific cross sections and rate coefficientsare computed over a wide range of collision energies and initial rovibrationalstates and subsequently incorporated into a master-equation frameworkto evaluate thermal and quasi-steady-state (QSS) rate coefficients,internal energy transfer, and dissociation energy removal. The resultsreveal strong mode-specific effects in dissociation kinetics. Forboth systems, dissociation rates increase sharply with internal energy;however, at fixed total energy, molecules with high vibrational energydissociate several orders of magnitude faster than those with lowvibrational energy but matched internal energy, demonstrating clearpreferential vibrational promotion. Bound–bound transitionsshow that higher-multiplicity potential energy surfaces significantlyenhance inelastic transition rates, particularly for large energygaps. Master-equation analysis indicates that vibrational and rotationalmodes relax on distinct time scales at low temperatures, with convergenceat higher temperatures driven by increased collisional efficiency.Comparison with data from literature reveals the importance of theinclusion of the sextet PES in accurately predicting the energy relaxationrates. These results provide detailed insight into energy transferand dissociation dynamics in the NO2 system and establisha physically consistent basis for reduced-order kinetic modeling undernonequilibrium conditions.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 39","pages":"7753–7772"},"PeriodicalIF":3.0,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124807","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}

引用次数: 0

Water Attachment onto Size-Selected Cationic Hydroxy–Pyrene Clusters 水附着在大小选择的阳离子羟基芘簇上

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-10-01 Epub Date: 2026-09-21 DOI: 10.1021/acs.jpca.6c05183

Sébastien Zamith, Alexandre Marciniak, Fatima Baterdouk, Aude Simon, Christine Joblin

{"title":"Water Attachment onto Size-Selected Cationic Hydroxy–Pyrene Clusters","authors":"Sébastien Zamith, Alexandre Marciniak, Fatima Baterdouk, Aude Simon, Christine Joblin","doi":"10.1021/acs.jpca.6c05183","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05183","url":null,"abstract":"We study the attachment of a single water molecule collidingwithcationic clusters of hydroxypyrene (PyOH)─a medium-sized hydroxylatedpolycyclic aromatic hydrocarbon (OH-PAH). The (PyOH)n+ clusters (n = 2–6) weregenerated using a cryogenic molecular cluster source. The attachmentrates are measured as a function of collision energy and initial clustertemperature. To rationalize the experimental results, we use a modelthat accounts for the dissociation rates of the water molecule in[(PyOH)nH2O]+ complexesto estimate the survival probability of these species. The derivedbinding energies range from ∼0.5 to 0.4 eV, decreasing withcluster size. By comparing our results with a previous study on pyreneclusters, we highlight the key role of charge combined with the hydroxylfunction in enhancing the stability of [(PyOH)nH2O]+ complexes at higher temperatures.These findings add a new piece to the chemical network driving thephysico-chemical evolution of PAHs and their role in planet-formingregions and exoplanetary atmospheres.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 39","pages":"7852–7861"},"PeriodicalIF":3.0,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093635","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}

引用次数: 0

Differences in the Initial Thermal Decomposition Mechanisms of Isomeric Nitrogen-Rich Energetic Compounds: A First-Principles Study of DTDA and T-N10B 富氮同分异构体含能化合物初始热分解机制的差异：DTDA和T-N10B的第一性原理研究

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-09 DOI: 10.1021/acs.jpca.6c03918

Zeyuan Chen, Guangrui Liu, Yahong Chen, Shuhai Zhang, Shuangfei Zhu

{"title":"Differences in the Initial Thermal Decomposition Mechanisms of Isomeric Nitrogen-Rich Energetic Compounds: A First-Principles Study of DTDA and T-N10B","authors":"Zeyuan Chen, Guangrui Liu, Yahong Chen, Shuhai Zhang, Shuangfei Zhu","doi":"10.1021/acs.jpca.6c03918","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c03918","url":null,"abstract":"As novel isomeric nitrogen-rich energetic materials (NREMs),1,2-di(2′H-[1,5′-bitetrazol]-5-yl)diazene (DTDA) and 2,2′-azobis(1,5′-bitetrazole)(T-N10B) have attracted considerable attention due to their excellentdetonation performance. In this study, first-principles moleculardynamics simulations were employed to systematically investigate thedifferences in their initial thermal decomposition mechanisms. Resultsshow that both T-N10B and DTDA share three major initial decompositionpathways, but T-N10B tends to initiate via inner/outer tetrazole ring-opening,while DTDA prefers H atom dissociation and inner ring-opening. Afterinitial decomposition, T-N10B releases large amounts of N2 in the subsequent two steps, whereas DTDA still undergoes extensiveH atom dissociation/transfer, leading to less N2 release.Notably, both molecules have specific tetrazole ring-opening sites.Furthermore, the significant H-transfer reactions during the earlystage and the better tetrazole ring stability are key to DTDA’ssuperior thermal stability, making it decompose more slowly than T-N10B.These findings will deepen the understanding of the energy releasemechanism of tetrazole-based NREMs and provide important insightsfor the design of novel NREMs.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 38","pages":"7579–7592"},"PeriodicalIF":3.0,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149027907","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}

引用次数: 0

Finding the Best Density Functionals for Water: Benchmarking the Forces 寻找水的最佳密度函数：力的基准。

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-01 DOI: 10.1021/acs.jpca.6c00577

Shifan Cui

引用次数: 0

Charge Migration in Cations: Structures, Energies, and Vibrational Frequencies of Ground and Excited States of HCCX+, CH3X+, Vinyl Bromide Cation and Propiolic Acid Cations 阳离子中的电荷迁移：HCCX+、CH3X+、乙烯基溴离子和丙酸阳离子基态和激发态的结构、能量和振动频率

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-10 DOI: 10.1021/acs.jpca.6c02409

Deep Mukherjee, Andrew S. Durden, Matthew R. Hermes, Marco Caricato, H. Bernhard Schlegel

{"title":"Charge Migration in Cations: Structures, Energies, and Vibrational Frequencies of Ground and Excited States of HCCX+, CH3X+, Vinyl Bromide Cation and Propiolic Acid Cations","authors":"Deep Mukherjee, Andrew S. Durden, Matthew R. Hermes, Marco Caricato, H. Bernhard Schlegel","doi":"10.1021/acs.jpca.6c02409","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c02409","url":null,"abstract":"Coherent superposition of ground and excited states ofcationscan produce ultrafast charge migration that can be monitored by attosecondtransient absorption, attosecond pump-IR probe, high harmonic spectroscopy,attosecond streaking, and strong field ionization. Vibrational motionon the ground and excited states of the cations leads to decoherenceand decay of charge migration. Computational modeling of charge migrationrequires suitable methods for calculating energy differences betweenthe electronic states of the cations and potential energy surfacesfor the ground and excited states of the cations. The performanceof CCSD, EOM-CCSD, EOMCC-IP, CASSCF, and MC-PDFT/L-PDFT has been examinedfor computing ionization energies, cation excitation energies, andharmonic vibrational frequencies for ground- and excited-state cations.Three sets of molecules that are relevant to charge migration wereselected to illustrate different aspects of the calculations: HCCI+ and HCCBr+ have degenerate ground and first excitedstate of the same symmetry; CH3I+ and CH3Br+ are subject to Jahn–Teller distortionin their ground state; charge migration in vinyl bromide cation andpropiolic acid cation involves the ground state and second excitedstate of the cations. CCSD is limited to the lowest energy state ofa given symmetry. EOM-CCSD can be used for excited states. Both areeasy to apply, “black box” methods. EOMCC-IP is an alternativethat is less expensive than EOM-CCSD and is suitable for both groundand excited states of cations with degenerate vibrational modes. CASSCFwith state averaging is needed for Jahn–Teller distortion cases.MC-PDFT is suitable for adding correlation energy to CASSCF and generallyimproves the CASSCF results. L-PDFT is required for the proper treatmentof cations with degenerate or closely spaced electronic states.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 38","pages":"7544–7558"},"PeriodicalIF":3.0,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022765","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}

引用次数: 0

Formation of TPTA-NaCl/KCl Hybrid Nanostructures on Metal Surfaces 金属表面上TPTA-NaCl/KCl杂化纳米结构的形成

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-14 DOI: 10.1021/acs.jpca.6c04206

Xinyue Zhang, Zikun Yang, Yansong Liu, Peichao Wang, Zhixin Hu, Hong-Ying Gao

{"title":"Formation of TPTA-NaCl/KCl Hybrid Nanostructures on Metal Surfaces","authors":"Xinyue Zhang, Zikun Yang, Yansong Liu, Peichao Wang, Zhixin Hu, Hong-Ying Gao","doi":"10.1021/acs.jpca.6c04206","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04206","url":null,"abstract":"Alkali metal salts, as co-adsorbates, are crucial inregulatingthe self-assembly of molecules on metal surfaces. In this study, wereport the self-assembled hybrid nanostructures formed by alkali metalsalts (NaCl, KCl) and 2,2′:6′,2″-terpyridine-4,4′,4″-tricarboxylicacid (TPTA) on Ag(111) and Cu(111) by a combined studyof scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy(XPS), and density functional theory (DFT) calculations. These hybridstructures exhibit distinct differences compared with the self-assembledstructures of pure TPTA. Specifically, NaCl preferentiallybinds to the carboxylic groups of TPTA on Ag(111), butto the terpyridine core of TPTA on Cu(111). In contrast,KCl interacts with both the carboxylic groups and the terpyridinecore of TPTA on Ag(111), but with only the carboxylicgroups of TPTA on Cu(111). Furthermore, the co-depositedNaCl/KCl facilitates the deprotonation and hinders the decarboxylationof TPTA on Ag(111) as compared with the bare TPTA case, but only facilitates the deprotonation on Cu(111). Overall,our results demonstrate that the co-adsorption of specific alkalimetal salts serves as an effective strategy to tune the binding modesand on-surface chemical reactions of molecules on different metalsubstrates.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 38","pages":"7609–7621"},"PeriodicalIF":3.0,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022687","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}

引用次数: 0

Mapping the Excited State Dynamics of Gas-Phase Spiropyran with Time-Resolved Photoelectron Spectroscopy 用时间分辨光电子能谱绘制气相螺吡喃的激发态动力学

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-10 DOI: 10.1021/acs.jpca.6c04049

Xuegang Liu, Shijie Zheng, Chuyuan Zhai, Jie Yang

引用次数: 0

Symmetry-Induced Topological Obstructions in Woodward–Hoffmann Forbidden Reactions: A Molecular Qubit Representation Woodward-Hoffmann禁止反应中对称诱导的拓扑障碍：分子量子位表示

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-15 DOI: 10.1021/acs.jpca.6c04534

Subha Sandeep Repaka, Thillaiarasi Sukumar, Bhagyashri Devaru Bhat, Ran Friedman, Baswanth Oruganti

{"title":"Symmetry-Induced Topological Obstructions in Woodward–Hoffmann Forbidden Reactions: A Molecular Qubit Representation","authors":"Subha Sandeep Repaka, Thillaiarasi Sukumar, Bhagyashri Devaru Bhat, Ran Friedman, Baswanth Oruganti","doi":"10.1021/acs.jpca.6c04534","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04534","url":null,"abstract":"Woodward–Hoffmann (WH) rules for electrocyclicreactionsremain to date one of the most successful predictive tools in theoreticalorganic chemistry. At the heart of these rules is the simple ideathat preserving bonding continuity in the highest occupied molecularorbital (HOMO) confers a kinetic advantage compared to a pathway thatinvolves bonding disruption. However, this interpretation has beenchallenged by a few examples of symmetry-forbidden reactions thatexhibit similar or lower kinetic barriers than corresponding allowedpathways. In this study, we develop a generalization of the WH rulesthrough two complementary group-theoretic formulations: the UnitaryEvolution Inaccessibility Theorem (UEIT) and the Topological Obstructionto Bonding Disruption Theorem (TOBDT). UEIT establishes that symmetry-forbiddenreactions correspond to dynamical inaccessibility between the initialand target states under symmetry-preserving unitary evolution, whilethe TOBDT demonstrates that disruption in bonding continuity in aforbidden reaction constitutes a symmetry-induced topological obstruction.Within the frontier orbital subspace, the TOBDT is realized througha molecular qubit framework in which the orbital mixing angle Θserves as a geometric descriptor of topological obstruction. Thisframework is verified through DFT and CASSCF calculations on fourprototype 6π-electrocyclization reactions spanning diradicaloidand zwitterionic classes of transition states (TSs). Our results demonstratethat ΔΘ─the change in Θ between the reactantand the TS─correctly distinguishes diradicaloid from zwitterionicpathways. Additionally, computed nucleus-independent chemical shift(NICSzz) profiles confirm the antiaromaticcharacter of diradicaloid TSs and the nonaromatic character of zwitterionicTSs, suggesting that the orbital symmetry restrictions may not beapplicable in the latter.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 38","pages":"7732–7743"},"PeriodicalIF":3.0,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022630","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}

引用次数: 0

Field-Induced Heterolytic Dissociation of Isolated HF and HCl 场诱导分离HF和HCl的异解离

IF 3 2区化学

The Journal of Physical Chemistry A Pub Date : 2026-09-24 Epub Date: 2026-09-10 DOI: 10.1021/acs.jpca.6c03765

Megan Grace, Avdhoot Datar

{"title":"Field-Induced Heterolytic Dissociation of Isolated HF and HCl","authors":"Megan Grace, Avdhoot Datar","doi":"10.1021/acs.jpca.6c03765","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c03765","url":null,"abstract":"The influence of static electric fields on the electronicstructureand dissociation behavior of the polar diatomics HF and HCl is investigatedusing quantum chemical calculations. Ground- and excited-state potentialenergy surfaces (PESs) are computed as a function of bond distanceand external electric field strength to examine field-induced modificationsof chemical bonding. The calculations reveal pronounced bond softeningand progressive destabilization of both molecules with increasingfield intensity. Notably, the ground-state PES of HCl becomes entirelydissociative at field strengths of approximately 500 MV/cm, whereasHF requires a substantially stronger field of nearly 720 MV/cm toinduce dissociation. This difference reflects the greater polarizabilityand weaker bond localization in HCl relative to HF, providing a molecular-scaleperspective on the contrasting macroscale acid strengths of the twospecies. Field-dependent dipole moments further demonstrate the strongerelectronic response of HCl to external perturbations, highlightinghow molecular polarizability drives electric-field-induced bond activation.Ultimately, these results map out a detailed picture of field-controlleddissociation in hydrogen halides, supporting the view that local electricfields generated by surrounding hydrogen-bonding networks play a keyrole in modulating bond activation and condensed-phase acidity.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 38","pages":"7570–7578"},"PeriodicalIF":3.0,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022678","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}

引用次数: 0