The Journal of Physical Chemistry A最新文献

{"title":"A Spectroscopic and Computational Study of Dyes Based on Carbazole and TPA Donors, and Indane-Based Acceptors","authors":"Amir Sohail,&nbsp;Pawel Wagner,&nbsp;Joseph I. Mapley and Keith C. Gordon*,&nbsp;","doi":"10.1021/acs.jpca.5c04213","DOIUrl":"10.1021/acs.jpca.5c04213","url":null,"abstract":"<p >Spectroscopic and computational analyses were employed to investigate a series of donor–acceptor dyes connected by a fused dithiophene (dctp) 4,4-dihexyl-4H-cyclopenta[2,1-b:3,4-b′]. The donor units employed were triphenylamine (TPA) and carbazole (Cbz), while the acceptor units included Indane-based 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (InOCN) and 1H-indene-1,3(2H)-dione (IndO). A charge-transfer (CT) transition was evident in the electronic absorption spectra between 17,300 and 15,000 cm^–1. Each dye exhibited a singlet state of CT emission across all of the dyes. Emission spectra were observed from 14,700 to 13,100 cm^–1. Resonance Raman spectroscopy (RRS) was utilized to experimentally validate the time-dependent density functional (TD-DFT) findings. Furthermore, the results reveal that CT in 2-((6-(9-ethylcarbazol-3-yl)-4,4-dihexylcyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)methylene)indene-1,3-dione (PX134) and 2-(2-((6-(9-ethylcarbazol-3-yl)-4,4-dihexylcyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)methylene)-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (PX135) occurs from the donor-π system to the acceptor, whereas in ((6-(4-(diphenylamino)phenyl)-4,4-dihexylcyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)methylene)indene-1,3-dione (PX137) and 2-(2-((6-(4-(diphenylamino)phenyl)-4,4-dihexylcyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)methylene)-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (PX138), it proceeds from the donor to the π-acceptor units. These compounds exhibited distinct solvatochromic behavior in their absorption and emission spectra. These variations are analyzed using Lippert–Mataga (LM), McRae (MR), and Weller plots, which indicate changes in dipole moments between the ground and excited states. The linear slopes derived from the LM, MR, and Weller plots suggest a well-defined CT process with minimal specific solvent interactions. Density functional theory (DFT) modeling also suggests a significant level of planarity across all four dyes, and the experimental Raman spectra closely match the calculated Raman spectra. Compared to IndO groups, malononitrile units induce a greater CT character in the spectral emission behavior of each molecule. Variable temperature (VT) study reveals a blue shift with the increase in temperature across all of the dyes, indicating no evidence of aggregation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 36","pages":"8346–8356"},"PeriodicalIF":2.8,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936252","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":"An Efficient and Robust Implementation of CASSCF Linear Response Theory","authors":"Tommaso Nottoli*,&nbsp;Lorenzo Lapi,&nbsp;Riccardo Alessandro,&nbsp;Ivan Giannì,&nbsp;Federica Pes and Filippo Lipparini*,&nbsp;","doi":"10.1021/acs.jpca.5c03618","DOIUrl":"10.1021/acs.jpca.5c03618","url":null,"abstract":"<p >We present a robust and efficient implementation of linear response theory for a Complete Active Space─Self-Consistent Field wave function. Our approach relies on the Cholesky Decomposition of the two-electron integrals, enabling the routine treatment of large molecular systems on standard hardware. It allows for the computation of both absorption energies and transition properties, as well as frequency-dependent molecular response functions. For both classes of properties, numerically stable and efficient algorithms have been developed. The capabilities of our implementation are demonstrated through the calculation of absorption spectra and molecular response properties of large systems with extended basis sets.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 36","pages":"8441–8452"},"PeriodicalIF":2.8,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936234","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":"Crossed-Beams and Theoretical Studies of the Multichannel Reaction O(3P) + 1,2-Butadiene (Methylallene): Product Branching Fractions and Role of Intersystem Crossing","authors":"Gianmarco Vanuzzo,&nbsp;Andrea Giustini,&nbsp;Adriana Caracciolo,&nbsp;Silvia Tanteri,&nbsp;Domenico Stranges,&nbsp;Marzio Rosi,&nbsp;Piergiorgio Casavecchia*,&nbsp;Nadia Balucani*,&nbsp;Maristella Di Teodoro,&nbsp;Sarah Nicole Elliott and Carlo Cavallotti*,&nbsp;","doi":"10.1021/acs.jpca.5c03937","DOIUrl":"10.1021/acs.jpca.5c03937","url":null,"abstract":"<p >The reactions of ground state oxygen atoms, O(³P), with unsaturated hydrocarbons (UHs) are relevant in the oxidation in different environments. They are usually multichannel reactions that exhibit a variety of competing product channels, some of which occur adiabatically on the entrance triplet potential energy surface (PES), while others occur nonadiabatically on the singlet PES that can be accessed via <i>intersystem crossing</i> (ISC). ISC plays a key role on the mechanism of these reactions, impacting greatly the product yields. Identification of all primary reaction products, determination of their branching fractions (BFs), and assessment of the role of ISC is central for understanding the mechanism of these reactions. This goal can be best achieved combining crossed-molecular-beam (CMB) experiments with universal, <i>soft</i> ionization, mass-spectrometric detection and time-of-flight analysis to high-level <i>ab initio</i> electronic structure calculations of triplet/singlet PESs and Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) computations of product BFs with inclusion of ISC effects. Over the years this combined approach was found to be rewarding and successful for O(³P) reactions with the simplest alkynes, alkenes, and dienes containing two, three, or four carbon atoms. Here, we report the full experimental and theoretical work on the reaction O(³P) + 1,2-butadiene that permits us to explore how the mechanism and product distribution vary when moving from O(³P) + allene (propadiene) to O(³P) + methylallene (1,2-butadiene) and when comparing this system to related C4 unsaturated systems, namely O(³P) + 1-butene and O(³P) + 1,3-butadiene. In the present CMB experiments at the collision energy of 41.8 kJ/mol we have observed and characterized nine different product channels. Synergistic <i>ab initio</i> transition-state theory-based master equation simulations coupled with nonadiabatic transition-state theory on the coupled triplet/singlet PESs were used for computing the product BFs and assisting the interpretation of the experimental results. Theoretical predictions and experimental results were found to be in overall good agreement. The finding of this work can be useful for the kinetic modeling of the oxidation of 1,2-butadiene and of systems involving 1,2-butadiene as an important intermediate.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 36","pages":"8278–8302"},"PeriodicalIF":2.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c03937","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936232","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":"Coalescence-Induced Growth Doping in a II–VI Magic Size Cluster","authors":"Hyunggu Kim,&nbsp; and ,&nbsp;Kevin R. Kittilstved*,&nbsp;","doi":"10.1021/acs.jpca.5c04100","DOIUrl":"10.1021/acs.jpca.5c04100","url":null,"abstract":"<p >The versatility and stability of semiconductor magic size clusters (MSCs) have been exploited to synthesize unique nanostructures with well-controlled dimensionality. Strategies to incorporate dopant ions such as transition metals into II–VI MSCs typically result in substitutional doping at surface sites. In this study, we investigate the speciation of Co²⁺ in ZnS MSCs using three different cation exchange reactions at moderate temperatures. Using electronic absorption spectroscopy and ligand field theory, we confirm in every scenario that Co²⁺ either substitutes at the surface, remains as a precursor in solution, or forms a Co-rich impurity. However, upon growth of the Co²⁺-doped ZnS MSCs at higher temperatures, we observe conversion of the surface Co²⁺ to internal sites. This observation is consistent with tetrahedral Co²⁺ coordinated to μ₄–S^2– based on comparison of the same transition observed previously with internally doped Co²⁺:ZnS QDs. We propose the internalization is due to a coalescence growth mechanism involving direct attachment, interface relaxation, and reshaping of the Co²⁺-doped ZnS MSCs in contrast to typically observed stepwise MSC growth or Ostwald ripening in doped QDs.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 36","pages":"8324–8336"},"PeriodicalIF":2.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936245","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":"Constructing NIR-II Fluorophores with Enhanced Fluorescence Quantum Efficiency via Asymmetric D-A-D′ Molecular Architectures","authors":"Lingling Dong,&nbsp;Jing Zhang,&nbsp;Wei Hu and Yujin Zhang*,&nbsp;","doi":"10.1021/acs.jpca.5c04450","DOIUrl":"10.1021/acs.jpca.5c04450","url":null,"abstract":"<p >Organic donor–acceptor–donor (D-A-D) fluorophores with emission in the second near-infrared (NIR-II) window have attracted growing attention for bioimaging applications. While incorporating strong electron donor and acceptor units into the molecular framework enables long-wavelength emission, it inevitably leads to a decrease in the fluorescence quantum efficiency (FQE). Herein, we investigated the microscopic mechanism underlying luminescent efficiency enhancement in NIR-II chromophores featuring asymmetric D-A-D′ molecular architectures. Based on a typical D-A-D scaffold, a series of compounds is designed through unilateral and bilateral heteroatom substitutions. It indicates that two independent intramolecular charge transfer transitions from different donors to the acceptor are responsible for the photophysical performances of the D-A-D′ fluorophores, resulting in balanced spectral shift and FQE as compared to the D-A-D and D′-A-D′ counterparts. Notably, the reduction of the nonradiative decay rate arising from the decreased nonadiabatic coupling and electron–vibration coupling caused by suppressed vibrational relaxations mainly contributes to the enhanced FQE, which exhibits a strong correlation with the adiabatic excitation energy of the compounds. With unilateral heteroatom substitution at the ortho-position, Fluo 2′ achieves optimal NIR-II emission and FQE, making it a promising candidate for NIR-II imaging. These findings highlight the dual-pronged design strategy for optimizing the luminescent performances of the NIR-II fluorophores, which facilitates the development of highly efficient chromophores for biomedical imaging applications.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 36","pages":"8370–8379"},"PeriodicalIF":2.8,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936271","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":"On the Chlorobenzene-Ammonia Cluster Reaction: Entrance Channel Dynamics, 2CR2PI Spectroscopy, and Ion Imaging of the Reaction Dynamics","authors":"Ronald Mutete,&nbsp;Damian Kokkin,&nbsp;Natan Fessahaye,&nbsp;Thomas R. Howell,&nbsp;Richard A. Loomis and Scott A. Reid*,&nbsp;","doi":"10.1021/acs.jpca.5c02264","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02264","url":null,"abstract":"<p >Prior studies of halobenzene–ammonia complexes have shown that the nature of the cationic intermediate (i.e., Wheland-type vs ion-radical) may play a key role in determining the reaction products. To probe this link, we report here the reaction dynamics of the chlorobenzene-ammonia 1:1 complex (PhCl···NH₃) using product ion imaging following two-color resonant two-photon ionization. A threshold value of 8.863 ± 0.008 eV was determined for the appearance of protonated aniline, which accompanies Cl atom loss and is the dominant product channel at energies near threshold. Scanning down to energies close to threshold, we find no evidence for a roaming halogen radical mechanism leading to HCl products, which was evidenced in the related bromobenzene–ammonia complex, and proceeded through an ion-radical intermediate structure. Here, supporting calculations indicate that both types of intermediates are present, but the Wheland-type structure is significantly more stable. Addressing a key question of earlier work, analysis of the PhCl···NH₃ potential energy surface (PES) in the reactant region establishes a complicated entrance channel pathway linking the in-plane σ-type complex to the Wheland intermediate (iWH) on the [PhCl···NH₃]^+• cationic surface. This pathway involves stepwise transition of the weakly bound ammonia from the initial in-plane σ-type complex to an <i>ortho</i> Wheland intermediate, followed by rearrangement to the <i>ipso</i> position. Finally, given that fluorine has been shown to stabilize aromatic ions, we hypothesized that fluorine substitution might alter the structure of the intermediate, favoring the ion-radical intermediate. To test this hypothesis, as an illustrative example the PES of the <i>meta</i>-PhClF-NH₃ system on the cationic surface was computed. Confirming our hypothesis, these calculations show an inversion in stability for the Wheland-type and ion–radical complex intermediates, with the latter preferred energetically at the examined level of theory.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 35","pages":"8056–8063"},"PeriodicalIF":2.8,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931479","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":"Quantitative Analysis of Virus Adsorption and Co-adsorption Behavior Using BET Modeling and SERS Spectroscopy","authors":"Jiaheng Cui,&nbsp;Yanjun Yang*,&nbsp;Amit Kumar,&nbsp;Jackelyn Murray,&nbsp;Les Jones,&nbsp;Xianyan Chen,&nbsp;Ralph A. Tripp and Yiping Zhao*,&nbsp;","doi":"10.1021/acs.jpca.5c03375","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03375","url":null,"abstract":"<p >Understanding virus–surface interactions is essential for developing effective biosensors, diagnostic tools, and antiviral strategies. In this study, we present a systematic investigation of the adsorption and coadsorption behavior of 12 respiratory viruses, including influenza, RSV, coronaviruses, adenovirus, and metapneumoviruses, using surface-enhanced Raman scattering (SERS) on SiO₂-coated silver nanorod array substrates. Both single viruses (SVs) and binary virus mixtures (2VMs) were analyzed in water and normal human saliva, and spectral data were modeled using a modified Brunauer–Emmett–Teller (BET) adsorption framework. Linear least-squares spectral decomposition enabled the extraction of adsorption coefficients that correlate with virus concentration and surface binding affinity. All viruses exhibited multilayer physisorption consistent with Type II isotherms, with the BET constant <i>q</i> varying substantially across virus types. Notably, 2VMs demonstrated a significantly enhanced adsorption behavior, often with <i>q</i> values 4–25 times greater than in SVs, indicating strong cooperative or competitive effects. Saliva modulated virus–surface interactions in virus-specific ways, emphasizing the complexity of adsorption dynamics in physiological environments. These findings highlight the limitations of single-virus calibration for quantitative detection in mixed-virus samples and underscore the need for mixture-aware analytical models in biosensing applications. This work provides a robust framework for mechanistic insight and quantitative modeling of virus adsorption relevant to real-world diagnostics and environmental monitoring.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 35","pages":"8204–8219"},"PeriodicalIF":2.8,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c03375","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931429","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":"Gas-Phase Benzene–Methanol Dimer Configurations: Geometries, Relative Stabilities, and Interaction Energies","authors":"Karl N. Kirschner*,&nbsp;","doi":"10.1021/acs.jpca.5c03923","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03923","url":null,"abstract":"<p >The benzene···methanol dimer is one of the simplest systems that manifests an O–H···π nonbonded interaction. This interaction can be found in numerous systems, ranging from small-molecule clusters to biological systems, for example, phenyl-containing ligands bound within a protein’s binding pocket. Herein, four gas-phase configurations are examined using quantum mechanics, which have O–H···π, CH₃···π and Bz–H···O interactions. Geometry optimization and frequency calculations were performed up to the MP2/aug-cc-pVQZ theory level, with electronic energies obtained up to the CCSD(T)/complete basis set (CBS) limit. Considering the electronic energy (Δ<i>E</i>_el), the O–H···π configuration is the most stable, with a CCSD(T)/CBS (counterpoise corrected) interaction energy of −4.09 kcal mol^–1, while the other three configurations ranged from −2.00 to −2.60 kcal mol^–1. Using scaled harmonic frequencies, the temperature influence was investigated by computing Gibbs relative and interaction free energies over a 10–800 K temperature range.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 35","pages":"8110–8119"},"PeriodicalIF":2.8,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931508","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":"Evaluating the Performance of the Exact Integral Simplified Time-Dependent Density Functional Theory (XsTD-DFT) to Compute One- and Two-Photon Absorption","authors":"Marilù G. Maraldi,&nbsp; and ,&nbsp;Marc de Wergifosse*,&nbsp;","doi":"10.1021/acs.jpca.5c03189","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03189","url":null,"abstract":"<p >Computing one-photon absorption and two-photon absorption (1PA and 2PA) of large molecular systems using an all-atom quantum mechanical (AQM) methodology presents significant computational challenges. This study evaluates the performance of the exact integral simplified time-dependent density functional theory (XsTD-DFT) method, a new recently introduced simplified quantum chemistry (sQC) approach that can be used as a key ingredient for AQM workflows to compute 1PA and 2PA. The <i>reliability</i>, <i>robustness</i>, and <i>computational efficiency</i> of the XsTD-DFT scheme are assessed against RI-CC2 reference calculations as well as with respect to TD-DFT results for a set of 91 organic molecules that includes systems from the QUEST database, medium-sized push–pull molecules, and small microhydrated clusters. The impact of various exchange–correlation functionals, basis sets, and the single energy threshold used to truncate the CIS space in the XsTD-DFT procedure is investigated. Results show that the XsTD-DFT method provides a substantial computational speed-up compared to TD-DFT, up to 3 orders of magnitude in CPU time with an energy threshold of 9 eV. The method robustly reproduces TD-DFT trends for excitation energies, oscillator strengths, and 2PA strengths. XsTD-DFT demonstrates reliability in capturing structure–property relationships and is reliable for nonequilibrium geometries as well as microhydrated systems. Comparisons with respect to experimental 1PA and 2PA spectra recorded in solution show similar agreements for the XsTD-DFT scheme than for TD-DFT. Guidelines for using the XsTD-DFT method in the context of 1PA and 2PA are provided. This study concludes that XsTD-DFT is a <i>reliable</i>, <i>robust</i>, and <i>computationally efficient</i> method to compute 1PA and 2PA, making it well-suited as a key ingredient for AQM workflows to treat realistic systems.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 35","pages":"8178–8203"},"PeriodicalIF":2.8,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931538","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":"Deciphering Neodymium Concentration-Dependent Structure-Thermodynamics Interplay in Molten LiF-NdF3 Salts: A Multiscale Mechanistic Exploration","authors":"Yuanyuan Wang,&nbsp;Yuanyuan Jiang,&nbsp;Shiqiang Cui,&nbsp;Xuejiao Li* and Yu Gong,&nbsp;","doi":"10.1021/acs.jpca.5c03292","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03292","url":null,"abstract":"<p >First-principles molecular dynamics simulations combined with differential scanning calorimetry experiments are employed to systematically elucidate how NdF₃ concentration modulates the structural and thermodynamic properties of molten LiF-NdF₃ (FLiNd) complexes─an important salt system unit for Generation IV nuclear reactor applications. Multiscale analysis unveils the concentration-dependent evolution of ionic pair or cluster architectures, electronic structures, phonon vibration modes, and thermophysical properties at operational temperatures, with particular emphasis on the ionic conduction mechanism of molten FLiNd. Preliminary observations suggest that the melting enthalpy depression may correlate with weakened cation–F interactions as NdF₃ concentration increases, percolation-limited transport appears to be predominantly influenced by NdF_<i>n</i>^3–<i>n</i> (<i>n</i> = 7 or 8) polyhedra, possibly due to enhanced electronic polarization effects, and emergent Nd–Nd–Nd networks could potentially contribute to phonon mode softening and a reduction in ionic conductivity. Overall, a predictive structure–property framework where electronic structure reorganization and lattice anharmonicity collectively govern the coordination structure and macroscopic transport is tentatively established, which provides quantitative guidance for optimizing fuel salt compositions and performance in molten salt reactors.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 35","pages":"8075–8084"},"PeriodicalIF":2.8,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931533","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}