Journal of Chemical Physics最新文献_第3页

Topological control of local electroneutrality in confined electrolytes. 受限电解质中局部电中性的拓扑控制。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0354344

Marcelo Lozada-Cassou

{"title":"Topological control of local electroneutrality in confined electrolytes.","authors":"Marcelo Lozada-Cassou","doi":"10.1063/5.0354344","DOIUrl":"https://doi.org/10.1063/5.0354344","url":null,"abstract":"Topology governs finite-size violations of local electroneutrality in confined electrolytes. Within Poisson-Boltzmann theory, we show that this topological control gives rise to a universal hierarchy of deviations in spherical, cylindrical, and planar confinement. We quantify this effect through an electroneutrality deviation ratio that captures the global electrostatic constraints associated with compactness and boundary multiplicity in Ωsph ≃ S2 × [0, δ], Ωcyl≃S1×R×[0,δ], and Ωslit≃R2×[0,δ]. Although local electroneutrality is asymptotically restored in the limit of infinite cavity size, finite-size deviations follow a robust topological hierarchy, being strongest in spherical cavities, weaker in cylindrical confinement, and weakest in planar slits. These results prove that topology is the organizing principle underlying confinement-induced charge redistribution and violations of local electroneutrality constitute a general electrostatic constraint governing overcharging, charge reversal, and long-range charge correlations. More fundamentally, they demonstrate that changing the topology modifies the global electrostatic constraints without altering the local Poisson-Boltzmann equations. As a counterintuitive manifestation of nonlinear confinement in a point-ion model, we report the existence of inside confinement charge reversal in charged hollow cylindrical and spherical nanoparticles. Since physically consistent, more general electrolyte theories must recover the Poisson-Boltzmann description in the appropriate limiting case, the present results establish a benchmark against which topological effects should be assessed beyond the Poisson-Boltzmann description.","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":"149164906","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

PolyFKAN: Integrating Fourier-KAN layers into graph neural networks for polymer property prediction. PolyFKAN：将傅里叶- kan层整合到图神经网络中用于聚合物性质预测。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0346557

Boran Li, Jiying Liu, Qi Yu, Zexi Yang, Yapeng Zhan

{"title":"PolyFKAN: Integrating Fourier-KAN layers into graph neural networks for polymer property prediction.","authors":"Boran Li, Jiying Liu, Qi Yu, Zexi Yang, Yapeng Zhan","doi":"10.1063/5.0346557","DOIUrl":"https://doi.org/10.1063/5.0346557","url":null,"abstract":"Graph neural networks have become a central tool for polymer property prediction, but their fixed activation functions can impose a low-pass spectral bias that smooths over the sharp, multi-scale structure-property variations that distinguish chemically similar polymers. We address this limitation with PolyFKAN, a multitask graph-learning architecture that augments the prediction head of a polyGNN backbone with Fourier Kolmogorov-Arnold network layers. PolyFKAN represents edge-wise activations as truncated Fourier series and couples the resulting spectral branch to the standard multilayer perceptron (MLP) pathway through a bounded residual gate, thereby increasing functional expressivity without disrupting the learned graph embeddings. Across 17 polymer properties spanning electronic, thermodynamic, optical/dielectric, thermal, and gas-permeability domains, PolyFKAN achieves statistically significant improvement over a tightly controlled polyGNN baseline on 11 of 17 targets (one-sided t-test, p < 0.05), with one additional target showing marginal improvement. The gains are especially pronounced for multi-scale properties, including more than 15% average root mean squared error reduction for large-penetrant gas permeabilities and more than 15% improvement across optical and dielectric targets. Hierarchical ablation further reveals that optimal Fourier bandwidth is property-dependent: difficult, multi-scale targets require broader spectral capacity with stronger amplitude control, whereas high-fidelity targets benefit from lighter regularization. These results establish Fourier-KAN prediction heads as a minimally invasive and physically aligned inductive bias for polymer informatics.","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":"149182146","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

Ultrafast spin-transfer dynamics and single-qubit logic gate design in monocyclic carbon rings with transition metal atoms adsorbed. 过渡金属原子吸附单环碳环的超快自旋转移动力学和单量子比特逻辑门设计。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0344787

Yan Wu, Shangjie Ma, Ronghua Chen, Shuai Xu, Yiming Zhang, Jing Liu, Chun Li, Georgios Lefkidis, Wolfgang Hübner, Wei Jin

{"title":"Ultrafast spin-transfer dynamics and single-qubit logic gate design in monocyclic carbon rings with transition metal atoms adsorbed.","authors":"Yan Wu, Shangjie Ma, Ronghua Chen, Shuai Xu, Yiming Zhang, Jing Liu, Chun Li, Georgios Lefkidis, Wolfgang Hübner, Wei Jin","doi":"10.1063/5.0344787","DOIUrl":"https://doi.org/10.1063/5.0344787","url":null,"abstract":"We present a first-principles study of ultrafast spin-transfer dynamics and single-qubit logic gate design in transition metal (TM) atom-adsorbed monocyclic carbon ring systems. The structure- and size-dependent features of geometries, electronic structures, and spin localizations are analyzed. Notably, the TM2-C4n+2 systems generally prefer out-of-plane configurations and exhibit localized states with spin localized singly on one TM atom or doubly on two TM atoms, rather than the carbon ring-related localized states found in the mostly coplanar TM-C4n+2 systems. Driven by well-tailored nonchirped ultrafast laser pulses, sub-picosecond, high-fidelity spin transfer is achieved in most structures (except for the ones with only one type of spin localized states). The laser detuning and chirp effects on these scenarios are further explored. The tolerance and sensitivity characteristics of them can provide valuable guidance for both experimental implementation and sensor applications. In addition, based on the achieved ultrafast dynamics for the representative structures FeC14 and Fe2C18, four basic single-qubit quantum logic gates Pauli X, Pauli Y, Pauli Z, and S are all constructed, with an additional non-Clifford T gate achieved in the latter one. All these results demonstrate the great potential of the TM atom adsorbed carbon ring structures and provide significant guidance for experimental realization of the ultrafast spin dynamics and design of carbon-based molecular spintronic devices toward quantum computing.","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":"149181483","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

Algorithmic construction and exploitation of topology-constrained refinement models for semiexperimental equilibrium structures. 半实验平衡结构拓扑约束细化模型的算法构建与开发。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0353320

Vincenzo Barone

{"title":"Algorithmic construction and exploitation of topology-constrained refinement models for semiexperimental equilibrium structures.","authors":"Vincenzo Barone","doi":"10.1063/5.0353320","DOIUrl":"https://doi.org/10.1063/5.0353320","url":null,"abstract":"Semiexperimental equilibrium structures combine high-resolution rotational spectroscopy with computed vibrational and electronic corrections. Although the least-squares solution is well established, constructing the inverse model still requires expert choices of coordinates, symmetry, constraints, and parameter classes. We introduce MORPHEUS (Model Optimization and Refinement from Perceived Hierarchy, Equivalence, Uncertainty, and Symmetry), a reproducible framework that makes these choices explicit and tests them against topology, symmetry, rank, isotope coverage, and external reference information. Starting from Cartesian geometry, it builds non-redundant internal coordinates and a refinement model before fitting. Two alternative active spaces are supported: symmetry-adapted generalized internal coordinates and symmetry-adapted Cartesian displacements with translations and rotations removed. Across acyclic, cyclic, planar, fused, bridged, and flexible molecules, the workflow recovers effective dimensions, residuals, structural parameters, and uncertainties without manual construction of the active coordinate model. In camphor, the chemically validated model gives sub-milliangstrom bond corrections and remains stable under basis changes, robust losses, predicate-width scans, and multi-starts. A 49-atom testosterone demonstration shows how QC geometries, accelerated vibrational corrections, and class-constrained refinement models can be combined when isotope-rich data are unavailable.","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":"149182138","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

Cooling down trees for finite-temperature quantum dynamics: Purification within ML-MCTDH. 有限温度量子动力学的冷却树：ML-MCTDH内的净化。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0355267

Niclas Krupp, Oriol Vendrell

{"title":"Cooling down trees for finite-temperature quantum dynamics: Purification within ML-MCTDH.","authors":"Niclas Krupp, Oriol Vendrell","doi":"10.1063/5.0355267","DOIUrl":"https://doi.org/10.1063/5.0355267","url":null,"abstract":"Simulating multidimensional quantum systems at finite temperature is inherently challenging as the system is no longer described by a single, pure-state wavefunction but by a density operator, squaring an already exponential scaling of the Hilbert space. Building upon the compact wavefunction ansatz of the multi-layer multiconfiguration time-dependent Hartree (ML-MCTDH) method, we present a new scheme for simulating finite-temperature quantum dynamics based on purification. Here, a density operator is mapped to a single ML-MCTDH wavefunction in an enlarged Hilbert space, comprising physical and auxiliary degrees of freedom. In the key step, one obtains a pure-state representation of the canonical density operator via imaginary time-propagation of the infinite-temperature state. The most important observation is that this state can be exactly decomposed as a Hartree product of maximally entangled combined modes, each combined mode consisting of a physical degree of freedom and its auxiliary counterpart. Through dynamically pruning the node ranks of the ML-tree during the \"cool down\" stage yields a compact finite-temperature wavefunction, thus accelerating the real-time propagation and enabling finite-temperature simulations of multidimensional, correlated molecular systems. Our method circumvents both intensive statistical sampling and costly tensor-decomposition of the full density-operator, while being broadly applicable to model Hamiltonians and general ab initio potential energy surfaces alike. Two applications of the method are presented: benchmark results on the thermal ground-state of H2O, as well as temperature-dependent infrared absorption spectra of the more challenging, floppy H3O2- anion.","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":"149182209","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

Electronic spectroscopy of (N2O)n+ (n = 2-6): Competition between the charge resonance and charge transfer bands. （N2O）n+ (n = 2-6)的电子能谱：电荷共振带和电荷转移带之间的竞争。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0354431

Mitsuaki Shioura, Asuka Fujii

引用次数: 0

Multi-state switching of topological magnetic textures via enhancing ferroelectric polarization in van der Waals multiferroic heterostructure LaBr/In2Se3. 范德华多铁异质结构LaBr/In2Se3中增强铁电极化的拓扑磁性织构的多态切换。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0333428

Churen Gui, Han Pan, Bo Huang, Shu-Zong Li, Zhenqing Li, Jun Chen, Wei-Bing Zhang

{"title":"Multi-state switching of topological magnetic textures via enhancing ferroelectric polarization in van der Waals multiferroic heterostructure LaBr/In2Se3.","authors":"Churen Gui, Han Pan, Bo Huang, Shu-Zong Li, Zhenqing Li, Jun Chen, Wei-Bing Zhang","doi":"10.1063/5.0333428","DOIUrl":"https://doi.org/10.1063/5.0333428","url":null,"abstract":"Topological magnetic textures hold great promise for non-volatile memory applications, owing to their topological stability and low energy consumption. Conventional manipulations focus on the creation/annihilation of one topological state or switching between two states, however, the multi-state switching remains largely unexplored. Here, we proposed that enhancing ferroelectric polarization can drive multi-state switching of topological magnetic textures, as evidenced in van der Waals multiferroic heterostructures LaBr/In2Se3. Using first-principles calculations and micromagnetic simulations, we revealed that increasing In2Se3 thickness triggers phase transitions among three distinct topological magnetic textures, including bimeron, trimeron, and skyrmionium-like structure. The intrinsic mechanism of the phase transitions originates from the competition among LaBr's exchange interaction, Dzyaloshinskii-Moriya interaction, and magnetic anisotropy energy, which are significantly tuned by the enhanced ferroelectric polarization of In2Se3. Our work offers a theoretical guidance for voltage-controlled multi-state switching of topological magnetic textures, which sheds lights on the applications of topological spintronics.","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":"149182119","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

Low-energy electron collisions with BH. 低能电子与黑洞碰撞。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0354874

R Mezlini, F Iffly, D Hvizdos, J Zs Mezei, A E Orel, Å Larson, I F Schneider

{"title":"Low-energy electron collisions with BH.","authors":"R Mezlini, F Iffly, D Hvizdos, J Zs Mezei, A E Orel, Å Larson, I F Schneider","doi":"10.1063/5.0354874","DOIUrl":"https://doi.org/10.1063/5.0354874","url":null,"abstract":"BH+ ions are expected to play an important role in boron-containing plasmas relevant to fusion environments such as ITER, where low-energy electrons drive a variety of inelastic and reactive scattering processes. In particular, dissociative recombination, vibrational excitation, and de-excitation strongly influence the ion balance and energy distribution in such plasmas. We present a theoretical study of electron collisions with BH+ using a combination of ab initio electronic structure calculations and electron scattering methods. Potential energy curves for bound states of BH and BH+ are obtained using multireference configuration interaction, while autoionization widths of electronic resonant states are computed with the complex Kohn variational method. The collision dynamics is modeled within multichannel quantum defect theory, including both the \"crossing\"-i.e., Feshbach-resonances-mediated-and the \"non-crossing\"-i.e., Rydberg-mediated-mechanisms. Cross sections and thermal rate coefficients for the processes are provided for the lowest vibrational levels of BH+ and its isotopologues-BD+ and BT+-showing significant isotope effects, especially at low electron temperatures.","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":"149182164","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

Local chemical softness as a reactivity probe in mixed-valence compounds of class I and class II (Cr2F5 and Co3O4): The importance of site-dependent Hubbard U parameters. 局部化学软性作为ⅰ类和ⅱ类混合价化合物（Cr2F5和Co3O4）的反应性探针：位点依赖性Hubbard U参数的重要性

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0342191

Josseline Aguilar-López, Guadalupe Castro, Marcelo Galván

{"title":"Local chemical softness as a reactivity probe in mixed-valence compounds of class I and class II (Cr2F5 and Co3O4): The importance of site-dependent Hubbard U parameters.","authors":"Josseline Aguilar-López, Guadalupe Castro, Marcelo Galván","doi":"10.1063/5.0342191","DOIUrl":"https://doi.org/10.1063/5.0342191","url":null,"abstract":"In this work, we employ local softness as a key reactivity descriptor to systematically analyze class I (Cr2F5) and class II (Co3O4) mixed-valence materials. We evaluated the performance of several exchange-correlation functionals, including PBEsol, NCAPR (Nearly Correct Asymptotic Potential Revised), SCAN (Strongly Constrained and Appropriately Normed), and PBE+U (Perdew-Burke-Ernezerhof + Hubbard U), to determine their ability to resolve electron donor and acceptor capacities. Our results demonstrated that local softness is a powerful tool for distinguishing non-equivalent metallic centers and coexisting oxidation states. Crucially, we found that the PBE+U functional, utilizing site-specific Hubbard parameters (U) calculated via density functional perturbation theory, is the most robust approach, consistently reproducing the expected one-electron transfer. This study highlights the necessity of integrating local reactivity descriptors with differentiated Hubbard corrections for the accurate design and characterization of redox-active functional materials.","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":"149182195","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

Path dependence in alchemical calculations of water chemical potential in aqueous electrolytes. 水电解质中水化学势的炼金术计算中的路径依赖。

IF 3.7 2区化学

Journal of Chemical Physics Pub Date : 2026-10-14 DOI: 10.1063/5.0342824

Arlind Kacirani, Betül Uralcan, Amir Haji-Akbari

{"title":"Path dependence in alchemical calculations of water chemical potential in aqueous electrolytes.","authors":"Arlind Kacirani, Betül Uralcan, Amir Haji-Akbari","doi":"10.1063/5.0342824","DOIUrl":"https://doi.org/10.1063/5.0342824","url":null,"abstract":"Accurate calculation of free energies and their derivatives is central to assessing the thermodynamic stability of molecular and particulate systems across length scales. Yet, such quantities can be difficult to compute reliably in strongly interacting systems, such as solutions of ionic species in polar solvents. One important example is the chemical potential of water in aqueous electrolytes, which can be estimated through staged particle insertion by gradually coupling an inserted molecule to its environment. Although the resulting insertion free energy should be independent of the alchemical pathway, the order and manner in which van der Waals and electrostatic interactions are activated can strongly affect convergence and, in some cases, yield inconsistent estimates. Here, we examine this issue by calculating water's chemical potential in aqueous KCl solutions using eight alchemical insertion pathways that differ in the extent and order of van der Waals and Coulombic coupling. We find that concurrently activating these interactions, particularly in fully coupled and partially end-coupled protocols, can produce chemically implausible insertion free energies. These anomalies arise within the soft-core Hamiltonian from intermediate states in which the inserted water molecule develops strong electrostatic interactions with a chloride ion before sufficient short-range repulsion has been established. In contrast, pathways that activate short-range van der Waals interactions before electrostatics yield more consistent and chemically plausible estimates. These findings demonstrate that practical alchemical calculations in polar and ionic environments can be highly sensitive to pathway design, underscoring the importance of decoupling short-range and electrostatic interactions in staged insertion alchemical protocols.","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":"149169480","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