Journal of Chemical Physics最新文献_第4页

Material and thermal properties of MgCl2 molten salt by ab initio and machine-learning molecular-dynamics simulations. 用从头算和机器学习分子动力学模拟MgCl2熔盐的材料和热性能。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0356683

Roberto Llovera, María Andrea Barral, Verónica Vildosola, Florencia Cantargi, Claudio Pastorino

{"title":"Material and thermal properties of MgCl2 molten salt by ab initio and machine-learning molecular-dynamics simulations.","authors":"Roberto Llovera, María Andrea Barral, Verónica Vildosola, Florencia Cantargi, Claudio Pastorino","doi":"10.1063/5.0356683","DOIUrl":"https://doi.org/10.1063/5.0356683","url":null,"abstract":"We study the structural, thermophysical, and dynamical properties of molten MgCl2 over a wide temperature range using Ab Initio Molecular Dynamics (AIMD) and molecular dynamics simulations based on machine-learning interaction potentials (MLIPs). MLIPs can achieve near-AIMD accuracy at a fraction of the computational cost, enabling simulations of larger systems and longer timescales. This opens up the possibility of studying the system under out-of-equilibrium conditions, which in turn allows for the calculation of physical properties, such as the thermal conductivity or viscosity, that cannot be obtained reliably for the typical time and length scales accessible to AIMD. We follow two complementary approaches to develop and evaluate the MLIPs. First, we develop a Deep Potential (DP) from scratch using AIMD trajectories at different temperatures. Second, we also evaluate two out-of-the-box foundation models and a fine-tuned version of one of them. The fine-tuning is performed using configurations from the AIMD trajectories originally used to train the DP. We compare the predictions of the trained DP, the foundation models, and AIMD simulations with the available experimental data and provide a comprehensive calculation of the most important physical quantities of molten MgCl2. We compute densities, radial and angular distribution functions, thermal conductivity, heat capacity, viscosity, and diffusion coefficients over the 1000-1600 K temperature range. This range is relevant to important technological applications such as thermal energy storage, generation IV nuclear reactors, and concentrated solar power systems. Finally, we briefly review the accuracy and performance of the different MLIP versions used throughout the work.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149182156","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

Efficient deduction of encoded local response within a thermodynamically perturbed folded protein. 热力学扰动折叠蛋白内编码局部响应的有效推导。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0350148

Mandira Dinda, Pallab Dutta, Manasvini Subramanian, Neelanjana Sengupta

{"title":"Efficient deduction of encoded local response within a thermodynamically perturbed folded protein.","authors":"Mandira Dinda, Pallab Dutta, Manasvini Subramanian, Neelanjana Sengupta","doi":"10.1063/5.0350148","DOIUrl":"https://doi.org/10.1063/5.0350148","url":null,"abstract":"Externally imposed perturbations can subtly reshape protein structure and mechanics prior to the emergence of global unfolding signatures. Delineating locally sensitive zones, however, can pose immense challenges. Subjecting a small folded protein to isotropic pressure spanning 0.001-10 kbar, we develop a simplified and interpretable computational framework to characterize local responses embedded within its conformational ensemble. Pairwise mechanical stiffness descriptors are treated as high-dimensional mechanical fingerprints and projected using linear discriminant analysis (LDA) to identify the pressure ranges that maximally separate conformational populations. To attribute the discriminative mechanical changes to specific residues, we combine the LDA model with SHapley Additive exPlanations, yielding a ranked set of locally responsive sites. While the overall rigidity landscape of the protein shows only modest pressure dependence, the top-ranked residues exhibit pronounced, pressure-specific alterations in solvent association. Radial distribution functions and tetrahedral order metrics reveal significant reorganization of hydration structure around the leading hotspot across the LDA-inferred transition region, whereas low-ranked sites display weak or nonspecific hydration changes. Together, these results connect global thermodynamic perturbation to localized mechanical and hydration responses and suggest a practical route for prioritizing mutation sites and mechanistic hypotheses in perturbed biomolecular systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149182214","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

Gate-controlled optical bistability via tunable self-action feedback in a semiconductor quantum dot-graphene nanodisk hybrid. 基于可调自作用反馈的半导体量子点-石墨烯纳米盘混合材料的门控光学双稳性。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0352299

Bintoro S Nugroho, Asifa Asri, Yudi Rosandi

{"title":"Gate-controlled optical bistability via tunable self-action feedback in a semiconductor quantum dot-graphene nanodisk hybrid.","authors":"Bintoro S Nugroho, Asifa Asri, Yudi Rosandi","doi":"10.1063/5.0352299","DOIUrl":"https://doi.org/10.1063/5.0352299","url":null,"abstract":"We theoretically examine how electrostatic gating can tune the steady-state response of a semiconductor quantum dot (SQD)-graphene nanodisk hybrid between monostable and bistable regimes. The model combines the optical Bloch dynamics of a driven two-level SQD with a gate-dependent polarizability of the graphene nanodisk. Through this polarizability, the gate voltage controls the SQD self-action, represented by the complex feedback parameter G(Vg) = GR(Vg) + iGI(Vg). The bistable response results from saturation of the SQD transition combined with graphene-mediated feedback. As Vg is varied, G(Vg) traces a trajectory in the complex feedback plane relative to the saddle-node boundary. Bistability occurs only along the part of this trajectory for which the steady-state input-output relation has two physical turning points. Within this segment, adiabatic sweeps of gate voltage or input intensity remain on a stable branch until a turning point is reached, giving a hysteresis loop. The stability of these branches is verified from the local Jacobian eigenvalues. The same turning-point criterion locates the gate-detuning domain for fixed-input branch switching and identifies the coupling-dephasing window in which the feedback trajectory can reach the bistable domain. These results identify gate-controlled complex self-action as the mechanism governing the opening and closing of the bistability window and the associated branch switching in the SQD-graphene nanodisk hybrid.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149166882","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

Inclusion of three-body corrections in the relativistic equation-of-motion coupled cluster method: Application to electron detachment. 相对论运动方程耦合簇方法中包含三体修正：在电子分离中的应用。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0335609

Mrinal Thapa, Achintya Kumar Dutta

{"title":"Inclusion of three-body corrections in the relativistic equation-of-motion coupled cluster method: Application to electron detachment.","authors":"Mrinal Thapa, Achintya Kumar Dutta","doi":"10.1063/5.0335609","DOIUrl":"https://doi.org/10.1063/5.0335609","url":null,"abstract":"We present the formulation and implementation of a triples-correction scheme for relativistic equation-of-motion coupled-cluster calculations of ionization potentials. Both full and partial triples-correction schemes are implemented using the exact two-component atomic mean-field (X2CAMF) Hamiltonian in combination with Cholesky decomposition (CD) of two-electron integrals and a frozen natural spinor (FNS) truncation scheme to reduce computational cost. Benchmark calculations on halide anions, noble-gas atoms, hydrogen halides, and dihalogen molecules demonstrate the importance of triple excitations for the quantitative prediction of ionization potentials. The CCSD(T)(a)* scheme achieves a mean absolute error of ∼0.01 eV relative to full CCSDT for halide anions and noble-gas atoms and ∼0.08 eV relative to the experiment for dihalogen molecules. The X2CAMF approximation reproduces four-component Dirac-Coulomb results with negligible deviations, while the CD-FNS strategy substantially reduces the computational cost. The resulting partial triples-correction scheme scales as O(n7) with storage comparable to CCSD, providing an accurate and practical approach for relativistic ionization-energy calculations in heavy-element systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149167065","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

Structural and energetic signatures of SO2 and CH4 incorporation in imidazolium-based ionic liquids. 咪唑基离子液体中SO2和CH4掺入的结构和能量特征。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0351322

Hugo Marques, José Nuno Canongia Lopes, Adilson Alves de Freitas, Karina Shimizu

{"title":"Structural and energetic signatures of SO2 and CH4 incorporation in imidazolium-based ionic liquids.","authors":"Hugo Marques, José Nuno Canongia Lopes, Adilson Alves de Freitas, Karina Shimizu","doi":"10.1063/5.0351322","DOIUrl":"https://doi.org/10.1063/5.0351322","url":null,"abstract":"A systematic molecular dynamics study of sulfur dioxide (SO2) and methane (CH4) incorporation in 24 imidazolium-based ionic liquids is presented, spanning different anion families and cation alkyl chain lengths. The two gases represent limiting cases of solvation behavior in ionic liquids: SO2 exhibits strong electrostatic interactions and Lewis amphoteric character, whereas CH4 is governed primarily by weak London dispersion forces. Radial distribution functions, coordination numbers, cluster-size distributions, and interaction energies were analyzed to elucidate the molecular organization of the mixtures. The results show that neither SO2 nor CH4 substantially disrupts the polar network of the ionic liquids. SO2 partitions between the polar and nonpolar regions of the ionic liquid, leading to reduced self-association and more gas distributions, whereas CH4 preferentially occupies alkyl-rich regions and exhibits only weak self-association with minimal dependence on cation chain length. Interaction energy decomposition highlights the dominant role of electrostatics in SO2 solvation and the free volume-driven, weakly interacting nature of CH4 incorporation. These findings provide a molecular-level framework for rationalizing incorporation trends and for guiding the design of ionic liquids for gas separation, highlighting how polarity, anion charge distribution, and cation alkyl chain length can be tuned to enhance specific SO2 stabilization while controlling nonspecific CH4 accommodation in alkyl-rich free-volume domains.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149168907","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

Tensor train compression of molecular orbitals. 分子轨道的张量列压缩。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0327459

Ruslan A Mallaev, Dmitry Morozov, Dmitry Zheltkov, Michael R Perelshtein, Roman Ellerbrock

{"title":"Tensor train compression of molecular orbitals.","authors":"Ruslan A Mallaev, Dmitry Morozov, Dmitry Zheltkov, Michael R Perelshtein, Roman Ellerbrock","doi":"10.1063/5.0327459","DOIUrl":"https://doi.org/10.1063/5.0327459","url":null,"abstract":"This work systematically investigates the tensor train (TT) compressibility of grid-represented Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals across a range of molecular systems and TT formats (standard, quantized, and z-permuted quantized). To overcome limitations of current TT solvers, we employ a novel orthogonal tensor train cross approximation (TT-Cross-Orth) to decompose Hartree-Fock and DFT orbitals into TTs, enabling the study of large molecules. We find that the approximation error decreases exponentially with TT-rank for all systems studied and identify quantized tensor train as the most efficient TT format. Furthermore, we identify quasi-periodic and symmetric structures-including graphene, graphite layers, and polyalanine helices-as particularly favorable candidates exhibiting sublinear rank growth with system size. The tensor train approach automatically compresses quasi-symmetries and systems with symmetry defects, which makes it an attractive approach for materials science applications. TT-Cross-Orth enforces orthogonality during the decomposition, thereby improving stability and reducing the number of function evaluations compared to standard TT-Cross. These findings establish an empirical foundation for the development of scalable tensor network methods for HF and DFT.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149181314","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

Cluster-resolved associating-fluid theory for patch-geometry-dependent phase behavior in patchy particle mixtures. 斑块状颗粒混合物中斑块几何相关相行为的簇分辨关联流体理论。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0352520

Hamza Çoban, Alfredo Alexander-Katz

{"title":"Cluster-resolved associating-fluid theory for patch-geometry-dependent phase behavior in patchy particle mixtures.","authors":"Hamza Çoban, Alfredo Alexander-Katz","doi":"10.1063/5.0352520","DOIUrl":"https://doi.org/10.1063/5.0352520","url":null,"abstract":"The spatial arrangement of binding patches is a key design variable in programmable self-assembly because it determines which local motifs, network connectivities, and ordered states are accessible at equilibrium. Yet this geometric information is often lost in analytical theories of associating fluids, which typically distinguish particles by valence and interaction strength but not by local patch arrangement. This limitation is especially pronounced in quasi-two-dimensional and interfacial assemblies, where reduced coordination enhances the thermodynamic impact of steric and bonding constraints. Here, we present a cluster-resolved statistical associating fluid theory (SAFT-P) that promotes a chosen local cluster (superparticle) to an explicit thermodynamic degree of freedom. This approach preserves an analytical free-energy description while retaining local motif information. Using binary and ternary patchy mixtures on two-dimensional square lattices with identical valence but different patch arrangements, we show that local geometry can shift phase boundaries and bias demixing in ways that conventional monomer-level SAFT does not capture. In particular, SAFT-P predicts an excess-composition coexistence curve for a mixture of four-patch geometric isomers that conventional monomer-level SAFT cannot distinguish at matched valence and interaction strengths. We also test the theory on two-dimensional triangular and three-dimensional cubic lattices, which are included primarily to demonstrate the extensibility of the framework. SAFT-P therefore provides a practical route to connect nanoscale patch placement with mesoscopic assembly and macroscopic thermodynamics in patchy colloids and related interfacial assemblies.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149182142","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

Machine-learned, finite temperature Fermi-operator expansions suitable for GPUs and AI-hardware. 机器学习，有限温度费米算子扩展适用于gpu和人工智能硬件。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0347394

Stanislaw Kowalski, Christian F A Negre, Anders M N Niklasson, Kipton Barros, Joshua Finkelstein

{"title":"Machine-learned, finite temperature Fermi-operator expansions suitable for GPUs and AI-hardware.","authors":"Stanislaw Kowalski, Christian F A Negre, Anders M N Niklasson, Kipton Barros, Joshua Finkelstein","doi":"10.1063/5.0347394","DOIUrl":"https://doi.org/10.1063/5.0347394","url":null,"abstract":"We present several finite-temperature recursive Fermi-operator expansion schemes based on the second-order spectral projection (SP2) method. Our approach builds on a previous observation that the electronic structure problem, as formulated through a recursive SP2 expansion, can be mapped onto the architecture of a deep neural network. Using this perspective, we generalize SP2 to finite electronic temperatures by constructing machine learning models that determine optimized recursive expansion coefficients. The same approach is also applied to the prediction of the electronic entropy for fractional occupation numbers. The coefficients are trained for a specified chemical potential and electronic temperature and are not available in closed analytical form. However, by employing an appropriate affine rescaling strategy to the Hamiltonian matrix, we eliminate the need to retrain the model for different temperatures and chemical potentials. Our approach avoids explicit diagonalization and relies solely on highly optimized matrix-matrix multiplication kernels. Compared to state-of-the-art diagonalization, we achieve an order-of-magnitude speedup in the single-particle finite-temperature density matrix calculation for small and moderately sized matrices on modern graphics processing units and dense matrix multiply units.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149182169","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

High-performance parallel implementation of spin-free high-order coupled-cluster theories. 无自旋高阶耦合簇理论的高性能并行实现。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0351337

Yu Jin, Christopher Hillenbrand, Timothy C Berkelbach, Huanchen Zhai

{"title":"High-performance parallel implementation of spin-free high-order coupled-cluster theories.","authors":"Yu Jin, Christopher Hillenbrand, Timothy C Berkelbach, Huanchen Zhai","doi":"10.1063/5.0351337","DOIUrl":"https://doi.org/10.1063/5.0351337","url":null,"abstract":"High-order coupled-cluster theories with iterative triples (CCSDT), perturbative quadruples [CCSDT(Q)], and iterative quadruples (CCSDTQ) provide benchmark-quality correlation energies, but their steep computational scalings, O(N8), O(N9), and O(N10), together with the large memory requirements of high-order amplitude tensors, have historically limited their application to small molecules. In this work, we develop efficient open-source implementations of spin-restricted CCSDT (RCCSDT), RCCSDT(Q), and RCCSDTQ within the pyscf package and a Message Passing Interface (MPI)-based extension, distributed-cc. The shared-memory implementation combines compact triangular storage of the highest-order amplitude tensors with the multithreaded tensor contraction backend pytblis, enabling efficient use of modern many-core central processing unit (CPU) architectures. This design delivers near-ideal thread scaling up to 90 cores and achieves wall times shorter than or comparable to existing single-node implementations for representative benchmark molecules. We further extend RCCSDT, RCCSDT(Q), and RCCSDTQ to distributed-memory architectures using MPI-based algorithms. By distributing compact high-order amplitudes across MPI ranks and overlapping communication with computation through nonblocking data transfers, the distributed implementation achieves near-ideal strong scaling on up to 32 nodes, corresponding to ∼3000 CPU cores. These developments substantially extend the practical reach of canonical high-order coupled-cluster theory, enabling CCSDT and CCSDT(Q) calculations on systems with ∼100 correlated electrons in 450 orbitals and CCSDTQ calculations on systems with ∼50 correlated electrons in 115 orbitals. Applications to π-stacked noncovalent dimers, the CO dissociation energy of Cr(CO)6, and the Cope rearrangement of semibullvalene demonstrate that canonical high-order coupled-cluster benchmarks are now feasible for chemically realistic molecular systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172197","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

Distinguishing electrostatic from ion-specific effects at charged oxide/water interfaces by sum-frequency spectroscopy. 用和频光谱法区分带电氧化物/水界面上的静电和离子特异性效应。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0349446

Ling Zhou, Yuxuan Liu, Xinyi Liu, Xin Lin, Wei-Tao Liu

{"title":"Distinguishing electrostatic from ion-specific effects at charged oxide/water interfaces by sum-frequency spectroscopy.","authors":"Ling Zhou, Yuxuan Liu, Xinyi Liu, Xin Lin, Wei-Tao Liu","doi":"10.1063/5.0349446","DOIUrl":"https://doi.org/10.1063/5.0349446","url":null,"abstract":"Charged aqueous interfaces are ubiquitous, yet the ionic modulation of interfacial reactions is often empirically related to the bulk ion concentration without distinguishing pure electrostatic screening from ion-specific interactions. The Gouy-Chapman-Stern (GCS) model provides a mean-field description of the surface charge and ion distributions at such electrified interfaces, but direct experimental validation at the molecular level remains scarce. Here, we combine in situ sum-frequency spectroscopy of surface lattice vibrations with the modified Poisson-Boltzmann formalism to spectroscopically disentangle various ionic effects. Using the benchmark silica/water interface in NaCl solutions as a model system, we calibrated experimental deprotonation rates of surface silanol groups against the calculated surface proton concentrations. Below the Na+ concentration of ∼2 M, the apparent ion-induced acceleration of deprotonation is fully accounted for by electrostatic screening alone, with ion concentration dependence essentially reflecting the change in surface proton concentration. Above this threshold, the GCS model breaks down as ions specifically perturb the surface structure, causing the deprotonation rate to exceed the electrostatic prediction. This framework is further examined by calculations across different pKa values, ionic valences, and oxide species, providing a general basis for interpreting interfacial ionic effects beyond the mean-field limit.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 14","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149182145","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