The Journal of Physical Chemistry A最新文献

{"title":"Computational Study of the H2CS and H2CO Reactions with CCH: Mechanisms and Kinetic Implications for Interstellar Chemistry","authors":"Silvia Alessandrini,&nbsp;Luigi Crisci,&nbsp;Cristina Puzzarini","doi":"10.1021/acs.jpca.6c04860","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04860","url":null,"abstract":"<p>The high abundance of the ethynyl radical (CCH) in theinterstellarmedium (ISM) makes its reaction with thioformaldehyde (H₂CS) potentially important for understanding the chemistry of sulfur-containingmolecules and small carbon chains in cold environments. In this work,we present a comprehensive theoretical investigation of this gas-phasereaction through an accurate characterization of the correspondingreactive potential energy surface (PES). To determine reaction ratecoefficients and identify the most favorable reaction pathways underthe low-temperature and low-pressure conditions of the ISM, kineticsimulations are performed. To assess the reliability of the theoreticalapproach and elucidate the role of sulfur substitution, the analogousH₂CO + CCH reaction has been investigated at the same levelof theory and directly compared with available experimental kineticdata. Despite the markedly richer and more interconnected PES of thesulfur system, both reactions are overwhelmingly dominated by a barrierlessH-abstraction mechanism leading to HCS/HCO and acetylene, thus makingthe H₂CS + CCH reaction an inefficient source of the C₃H₂S isomers under interstellar conditions. Thecomparison with the oxygen analogue reveals both common mechanisticfeatures and important differences while validating the adopted computationalprotocol. Our study provides the first reliable kinetic characterizationof the H₂CS + CCH reaction, delivering rate coefficientssuitable for inclusion in astrochemical databases.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8772–8781"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330372","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":"Mechanistic Insight into Palladium-Catalyzed Trifunctionalization of Terminal Alkynes: Origin of Enantio- and Regioselectivity","authors":"Xuexiang Ma,&nbsp;You-Dong Shao,&nbsp;Chao Shan,&nbsp;Ke Tang,&nbsp;Xiangyang Cheng,&nbsp;Lingfei Hu,&nbsp;Aili Feng,&nbsp;Dongju Zhang","doi":"10.1021/acs.jpca.6c05669","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05669","url":null,"abstract":"<p>Density functional theory calculations were performedto investigatethe mechanism and factors affecting the enantio- and regioselectivityin the palladium-catalyzed trifunctionalization of terminal alkynes.Our calculations uncover a novel mechanistic pathway, which differsfrom the catalytic cycle proposed by experimental authors. This improvedmechanism highlights that CO₂ elimination does not takeplace inside the catalytic cycle but proceeds as an off-cycle step.The reaction proceeds sequentially via C–O oxidative addition,direct deprotonation, C–B bond formation, 1,2-metalate shift,and inner-sphere C–C reductive elimination. Compared with inner-sphereC–C reductive elimination, the outer-sphere pathway is disfavoredboth thermodynamically and kinetically. The direct deprotonation processis characterized as the rate-determining step of the reaction. Theexcellent enantioselectivity is rationalized by the noncovalent interactionsbetween the substrate and ligand. Regioselectivity is mainly controlledby steric effects.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8838–8849"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330257","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":"Toward Machine Learning Enhancement of Accelerated Surface Hopping with Scaled Spin–Orbit Couplings","authors":"Jakub Martinka,&nbsp;Mahesh Kumar Sit,&nbsp;Pavlo O. Dral,&nbsp;Jiří Pittner","doi":"10.1021/acs.jpca.6c06078","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c06078","url":null,"abstract":"<p>Surface hopping (SH) methods are typically employed tosimulateultrafast nonadiabatic processes, but long time scales often remainbeyond their reach. To address this, the accelerated SH scheme mitigatesthis limitation by scaling the driving forces of such processes, eithernonadiabatic couplings (NACs) in the case of internal conversion orspin–orbit couplings (SOCs) for intersystem crossing. However,obtaining the actual time constant requires extrapolation from severalensembles of trajectories with different scaling factors. This introducesa significant computational demand, often restricting the number oftrajectories per ensemble and, therefore, reducing the statisticalconfidence in the resulting time constant. In this work, we investigatethe accelerated scheme using silaethylene (CH₂SiH₂) as a case study, evaluating various population fitting methodsand extrapolation techniques. We trained machine learning models forpotential energy surfaces (PESs) and NACs, and extended our Rotate-Predict-Rotateapproach to fit SOCs. These models demonstrate high performance, yieldingpopulations within the confidence interval of the reference MR-CISD/SA-CASSCF(2,2)data; however, the extrapolation itself is highly sensitive to thefitted time constants, leading to discrepancies in the final timeconstant. Finally, we showcase and discuss how ML models can enhancethe reliability of an accelerated SH scheme.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8997–9008"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330351","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":"Topology-Dependent Hydrogen-Bond Cooperativity and Many-Body Stabilization in HSCN Oligomers","authors":"Mahadevappa Naganathappa,&nbsp;Sumalya Kaluva","doi":"10.1021/acs.jpca.6c04442","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04442","url":null,"abstract":"<p>Hydrogen-bond cooperativity plays a key role in determiningthestability and properties of molecular aggregates, yet the influenceof aggregation topology on its microscopic origin remains poorly understoodfor thiocyanic acid (HSCN). Here, the structural, energetic, electronic,and spectroscopic properties of HSCN oligomers (monomer–pentamer)with linear, ladder, and cyclic topologies were investigated usingdispersion-corrected density functional theory. Interaction energyand many-body decomposition analyses show that aggregate stabilizationis dominated by pairwise hydrogen-bond interactions, while cooperativemany-body effects increase systematically with cluster size and aremaximized in cyclic assemblies. Complementary QTAIM, NCI-RDG, andcharge-density-difference analyses reveal progressive strengtheningof the S–H···N hydrogen-bond network accompaniedby enhanced intermolecular polarization, without altering its closed-shellcharacter. These electronic signatures are consistently reflectedin the vibrational spectra through systematic red shifts of the S–Hstretching mode. Together, the energetic, real-space electronic, andspectroscopic results demonstrate that hydrogen-bond topology governsthe emergence of cooperative stabilization in HSCN oligomers, withcyclic architectures providing the most effective framework for collectivehydrogen-bond reinforcement.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8750–8762"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330397","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":"Anharmonic Vibrational Structure and Bound States of the He–CO2 van der Waals Complex","authors":"Larry Rodriguez,&nbsp;Michael Natalizio,&nbsp;Angel Vasquez,&nbsp;John Oliver Lobo,&nbsp;Olaseni Sode","doi":"10.1021/acs.jpca.6c04334","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04334","url":null,"abstract":"<p>We present a new flexible-monomer two-body <em>ab initio</em> potential energy surface for the He–CO₂ van derWaals complex, extending our studies of the Ne–CO₂, Ar–CO₂, and Kr–CO₂ complexesto the least polarizable and most weakly bound member of the series.The shallow, anisotropic interaction makes the intermolecular motionstrongly anharmonic and delocalized, such that local-mode excitationenergies cannot necessarily be identified with physically bound vibrationallevels. Curvilinear vibrational self-consistent field (VSCF) and vibrationalconfiguration interaction (VCI) calculations are therefore used primarilyto characterize intramolecular anharmonicity and mode coupling, whilethe floppy intermolecular states are treated quantitatively usingcoupled-channel <span>BOUND</span> calculations on vibrationally averagedeffective potentials. The bound-state calculations yield a dissociationenergy of <em>D</em>₀ = 16.106 cm^–1 and four excited <em>J</em> = 0 levels between 7.699 and15.001 cm^–1 relative to the ground state. In contrast,the VCI-derived local-mode stretching fundamental and the reportedovertone and combination features lie above the dissociation thresholdand should not be interpreted as ordinary bound levels. The intramolecularspectrum remains largely monomer-like: the VCI <em>ν</em>₃ band origin is in close agreement with the experiment,the characteristic CO₂ Fermi-resonance structure is retained,and the intramolecular bending degeneracy is predicted to be liftedby only ∼0.03 cm^–1. Both the direct and bound-statetreatments predict the experimentally observed positive sign of thecomplexation-induced <em>ν</em>₃ shift, althoughits magnitude remains sensitive to the vibrational treatment. Theseresults ultimately show that the low-energy spectrum of He–CO₂ is governed by large-amplitude motion near dissociation,thereby outlining the limits of local-mode descriptions for weaklybound complexes.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8732–8739"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330414","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":"Siloxane-Radical Species: Chemical Characteristics and Use for Mass Calibration in Aerosol Mass Spectrometry","authors":"Emily R. Rogers,&nbsp;Ray P. Bambha,&nbsp;Zachary A. Livingston,&nbsp;Judit Zádor,&nbsp;Jas H. Shahanand,&nbsp;Pyeongeun Kim,&nbsp;Kevin R. Wilson,&nbsp;Hope A. Michelsen","doi":"10.1021/acs.jpca.6c04791","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04791","url":null,"abstract":"<p>Mass spectra generated by volatilized particulates oftenspan awide range of masses, complicating mass calibration for high-resolutiontime-of-flight mass spectrometers. We used synchrotron-based vacuum-ultravioletphotoionization aerosol mass spectrometry (VUV-AMS) to demonstratethat conductive silicone tubing can be used to generate a range ofdistinct, isolated calibration peaks over the mass range suitablefor calibration of aerosol mass spectra. We generated vaporized siloxaneoligomers by heating tubing composed of polydimethylsiloxane (PDMS)to temperatures of 150–230 °C. The heated tubing was placedin line with a soot source. Soot particles efficiently adsorbed thesesiloxane species and transported them to the detection region of anaerosol mass spectrometer. We hypothesize that siloxane radicals arecatalytically formed on the heated copper oxide surface of the VUV-AMStarget. This calibration source promotes the formation of three seriesof substituted-siloxane-oligomer radicals and twenty-one recurringmass peaks (not including isotopologues) between 73 and 799 Da. Theseseries are associated with oligomers of the siloxane base unit attachedto a trimethylsilyl group ([SiO(CH₃)₂]_<em>n</em>Si(CH₃)₃), an SiOCH₃ group ([SiO(CH₃)₂]_<em>n</em>SiOCH₃), and an SiOH group ([SiO(CH₃)₂]_<em>n</em>SiOH). Based on our results and informationfrom the literature, we hypothesize that the latter two series preferentiallyform cyclic free radicals. Without the soot source, the heated siliconetubing nucleates some particles and generates a subset of the siloxaneradical peaks reported here. We verified the mass calibration fromthese species using a sample of five polycyclic aromatic hydrocarbons(PAHs) spanning the mass range of 178–300 Da, 2,5-dimethylfuran,which has a nominal mass of 96 Da, and known hydrocarbons from ethylenepyrolysis spanning the mass range of 165–374 Da. This calibrationsource provides a broad range of mass peaks for calibration with minimalmodification to existing experimental designs.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8972–8986"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330219","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":"Quasiclassical Trajectory Study of NH(3Σ–) + NH(3Σ–) Reactive Collisions: The Role of Vibrational Energy","authors":"Delvany G. de Castro,&nbsp;Lucas W. S. Crispim,&nbsp;Maikel Y. Ballester","doi":"10.1021/acs.jpca.6c06053","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c06053","url":null,"abstract":"<p>We present a quasiclassical trajectory study of the reactionNH(³Σ^–) + NH(³Σ^–) → N₂ + H + H to investigate therole of <em>vibrational</em> excitation of the reactants.Using the globalsix-dimensional DMBE potential energy surface for the singlet groundstate of N₂H₂ (Poveda, L. A.; etal. J. Chem.Phys., 2009, 131, 044309). we characterize the singlet-surface contributionto this reaction. We ran trajectories for NH(<em>v</em>, 1)colliding with NH(<em>v</em>′, 1), with <em>v</em> = 1–5, covering both the case where a single reactant carriesvibrational excitation (<em>v</em>′ = 0) and the casewhere both do (<em>v</em> = <em>v</em>′), fortranslational energies 0.1 ≤ <em>E</em>_tr/kcal mol^–1 ≤ 10. As in our previous study,the dominant product channel is N₂ + H + H, formed viacompeting one-step and two-step (N₂H-intermediate) microscopicmechanisms. At low translational energy, states in which both reactantsare vibrationally excited show a larger two-step contribution thanthe corresponding singly excited states. A comparison of three stateswith nearly matched total vibrational energy, (4, 0), (3, 1), and(2, 2), shows that the distribution of vibrational energy betweenthe reactants affects the mechanism branching: above a few kcal mol^–1, sharing the excitation between both reactants favorsthe one-step mechanism, whereas the enhanced two-step contributionat the lowest collision energies is specific to (2, 2). The vibrationalenergy content of the nascent N₂ increases markedly withreactant vibrational excitation. Reactive cross sections, excitationfunctions, and rate constants are also reported.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8875–8888"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330299","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":"Dissociation Dynamics of Protonated Nitroimidazoles: The Ortho Effect as the Mechanistic Trigger for Radical Formation","authors":"Jorge H. C. Basilio,&nbsp;Ricardo R. Oliveira,&nbsp;Fábio C. S. Nogueira,&nbsp;Nina D. Ortiz,&nbsp;Gilberto B. Domont,&nbsp;Alexander Dorn,&nbsp;Wania Wolff","doi":"10.1021/acs.jpca.6c04617","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c04617","url":null,"abstract":"<p>Substituted 5-nitroimidazoles are recognized as beingsignificantlymore effective in treating hypoxic tumors than their 4-nitroimidazoleisomers. While classical Quantitative Structure–Activity Relationship(QSAR) models point to electron affinity (EA) as the critical parameterfor this activity, recent gas-phase electron-attachment studies reveala paradox: isolated radical anions of 1-methyl-5-nitroimidazole (1M5NI)do not spontaneously fragment into essential cytotoxic species suchas NO^• and OH^• radicals. To resolvethis dilemma, we investigate the high-energy dissociation pathwaystriggered instead of activated during radiotherapy. Because theseradiosensitizers capture secondary electrons and are immediately protonatedin the acidic tumor microenvironment, we utilized Electrospray Ionization(ESI) Orbitrap mass spectrometry to generate the [M + H]⁺ species. This protonated closed-shell cation serves as a rigorousstructural and mechanistic analogue to map the reaction topology ofthe transient in vivo state. By comparing the protonated 1M5NI ([1M5NI+ H]⁺) and 2-methyl-4-nitroimidazole ([2M4NI + H]⁺) isomers through high-level computational modeling [DFT and CCSD(T)],we elucidate that while EA serves as the initial trigger, the protonatedstate is mandatory to unlock the fragmentation pathway. Crucially,the massive energy deposition inherent to radiotherapeutic environmentsprovides the necessary driving force to overcome the high-energy dissociationbarriers (&gt;3 eV), channeling the internal energy along a specificnormal mode of vibration to eject the cytotoxic radicals. These findingsprovide a fundamental physical chemistry basis for the clinical efficacyof 5-nitroimidazole drugs.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8763–8771"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330255","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":"Exploring the Energy Landscape of Hydroxide–Water Complexes","authors":"Chenrui Shao,&nbsp;Greta M. Jacobson,&nbsp;Anne B. McCoy","doi":"10.1021/acs.jpca.6c05833","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c05833","url":null,"abstract":"<p>The structures and energies of complexes of hydroxideions withtwo to five water molecules are explored at the DLPNO-CCSD(T)(-F12)level of theory. For complexes with two or three water molecules,the most stable structures have all of the water molecules forminghydrogen bonds to the hydroxide ion, oriented so as to form weak water–waterhydrogen bonds. For the complex with four water molecules, the lowestenergy structures with three and four water molecules bound to thehydroxide ion are nearly isoenergetic, with the complex with threewater molecules bound to the hydroxide ion roughly 10 cm^–1 lower in energy. This result is consistent with photoelectron andinfrared spectroscopy for this ion. For the larger complexes, thestructures with four water molecules in the first solvation shellare the lowest in energy, while structures with three water moleculesbound to the hydroxide ion and two in the second solvation shell resemblelow-energy isomers of (H₂O)₆. The effect ofthe introduction of harmonic zero-point energy on the relative energiesof these isomers is explored, and the sizes of the shifts in the relativeenergies with the addition of zero-point energy are attributed toa balance between increases in the frequencies of the intermolecularvibrations and decreases in the frequencies of the OH stretching vibrationswith increased hydrogen-bond strength. Finally, we find that DLPNO-CCSD(T)/aug-cc-pVTZcalculations reproduce the relative energies of the isomers of thesehydroxide–water complexes evaluated at the complete basis setlimit.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8850–8857"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330383","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":"Normal-Mode-Based Nudged Band (NM-NEB) Method: Retrieving Potential Energy Surface Information from Local Hessians to Improve Transition State Search","authors":"Shijun Liang,&nbsp;Zhongjun Zhou,&nbsp;Zexing Qu","doi":"10.1021/acs.jpca.6c02928","DOIUrl":"https://doi.org/10.1021/acs.jpca.6c02928","url":null,"abstract":"<p>Traditional nudged elastic band (NEB) methods often yieldunphysicalinitial paths due to the lack of curvature information from the potentialenergy surface (PES). To overcome this limitation, we propose a Normal-Mode-basedNEB (NM-NEB) method that only leverages Hessian matrices of reactantand product minima. Key PES information is extracted from the localHessian matrices of reactants and products via frequency calculations,and dominant reaction modes are identified using a Franck–Condonfactor-based vibrational mode matching strategy. By displacing reactantsand products along these modes, we obtain two improved end pointsnear the true transition state, from which a physically reasonableinitial path is constructed. Validation on 20 diverse benchmark reactionsat the B3LYP-D3/6–31G* level shows that NM-NEB achieves stableconvergence where Cartesian- and internal coordinate-NEB fail, withgeometric and energy errors within 0.1 Å and 1.0 kcal/mol, respectively.The mode-guided path also reduces optimization iterations and avoidsunphysical artifacts inherent in traditional interpolation. By leveragingonly local Hessian information at the end point minima, this strategyachieves robust and efficient transition state search and providesa promising approach for medium-to-large systems, with its reliabilityfully validated on 20 diverse small-molecule benchmark reactions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"130 44","pages":"8950–8959"},"PeriodicalIF":3.0,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149330358","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}