Journal of Chemical Physics最新文献_第2页

Decoupling of single-particle and collective dynamics in arrested phase-separating glassy mixtures. 阻滞相分离玻璃混合物中单粒子与集体动力学的解耦。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0322356

Konstantin N Moser, Christos N Likos, Vittoria Sposini

{"title":"Decoupling of single-particle and collective dynamics in arrested phase-separating glassy mixtures.","authors":"Konstantin N Moser, Christos N Likos, Vittoria Sposini","doi":"10.1063/5.0322356","DOIUrl":"https://doi.org/10.1063/5.0322356","url":null,"abstract":"We investigate the structure and dynamics of a hard colloid-star polymer mixture in the range of its arrested phase separation, where an incipient demixing transition is interfering with a nearby vitrification line, focusing on the protein limit (smaller hard component). Soft-hard mixtures present a rich dynamics, influenced by different parameters, such as the concentration of the soft and hard components, the softness of the potential, and the size ratio between the two components. Using coarse-grained molecular dynamics simulations, we characterize the single-particle and collective dynamics of the hard colloidal tracers in the soft glassy matrix. The hard tracers show diffusive behavior of the mean squared displacement accompanied by non-exponential relaxation of the intermediate scattering functions at intermediate length scales and non-Gaussian displacement distributions. Moreover, we show that the system exhibits features compatible with arrested phase separation or a precursor of the same, leading to population splitting and decoupling between self- and collective dynamics of the hard colloids. Overall, we demonstrate that the interplay between arrested phase separation and glassiness leads to complex, multiscale phenomena that strongly influence the dynamics of the hard additives in the arrested matrix formed by the soft colloids.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838603","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

Determination of the CO2 hydrate three-phase coexistence curve via molecular dynamics simulation. 用分子动力学模拟方法确定CO2水合物三相共存曲线。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0325832

Cristóbal Romero-Guzmán, Jesús Algaba, M M Conde, Manuel M Piñeiro, Felipe J Blas

{"title":"Determination of the CO2 hydrate three-phase coexistence curve via molecular dynamics simulation.","authors":"Cristóbal Romero-Guzmán, Jesús Algaba, M M Conde, Manuel M Piñeiro, Felipe J Blas","doi":"10.1063/5.0325832","DOIUrl":"https://doi.org/10.1063/5.0325832","url":null,"abstract":"Over the past decade, the phase equilibria of CO2 hydrates have been the subject of numerous molecular simulation studies. However, inconsistencies among these works-stemming from disparate molecular models, box geometries, and simulation protocols-have hindered direct comparison. Moreover, prior simulations have generally not reported the three-phase dissociation temperature, T3, under conditions that reliably suppress finite-size and intermolecular potential truncation artifacts, often because of limited system sizes and/or short cutoff distances. Here, we compute T3 using molecular simulations specifically designed to minimize these effects, employing systems containing more than 3000 molecules and a long cutoff of 1.6 nm. The hydrate-aqueous-liquid CO2 coexistence temperature is obtained via the solubility method: at fixed pressure, we evaluate the CO2 solubility in the aqueous phase in contact with a CO2 hydrate phase and, separately, with a pure liquid CO2 phase over a range of temperatures. The intersection of the two solubility curves defines T3. This approach has emerged in recent years as an alternative and complementary method to direct coexistence. We apply this procedure from 100 to 5000 bar. In addition, we refine the unlike CO2-water interactions to reproduce the dissociation line quantitatively. We find that modifying the Berthelot combining rule for CO2-water cross-interactions with a scaling factor ξ = 1.085 yields excellent agreement between simulated T3 values and experimental ones, providing a qualitative description of the dissociation enthalpy along the line. Furthermore, we provide, to the best of our knowledge, the first physical explanation for the unusual reentrant behavior of the CO2 hydrate dissociation line. We show that this behavior originates from a pressure-induced change in the sign of the reaction molar volume, caused primarily by the strong compressibility of the fluid CO2 phase relative to the hydrate and aqueous phases.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838619","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

Twisted intramolecular charge transfer in betaine B30. 甜菜碱B30分子内扭曲电荷转移。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0319036

William W Parson, Rathiesh R Pandian, Zoey A Lockwood, Clemens Burda

{"title":"Twisted intramolecular charge transfer in betaine B30.","authors":"William W Parson, Rathiesh R Pandian, Zoey A Lockwood, Clemens Burda","doi":"10.1063/5.0319036","DOIUrl":"https://doi.org/10.1063/5.0319036","url":null,"abstract":"Transient ground-state bleaching (GSB), stimulated emission (SE), and excited-state absorbance (ESA) are measured for betaine-30 (B30) in the first excited singlet state (S1) on picosecond time scales. In the viscous solvents glycerol, ethylene glycol, and deep eutectic solvents with intermediate viscosities, SE is seen to the red of the ground-state absorption band and ESA at shorter wavelengths. By contrast, SE is not seen in the nonviscous solvents acetone and ethyl acetate, although both GSB and ESA are prominent. Fluorescence is detectable at room temperature in ethylene glycol and glycerol and increases as the temperature is lowered but is not seen in acetone or ethyl acetate. The absence of SE and fluorescence in nonviscous solvents is consistent with previous suggestions that S1 can relax to a conformation in which radiative transitions to the ground state (S0) are forbidden. Viscous solvents evidently suppress this relaxation. Time-dependent DFT calculations for B30 in various solvents show that the relaxed configuration is strongly twisted. Molecular orbitals, excitation energies, and oscillator strengths are calculated for structures on minimum-energy paths for twisting using six different density functionals, including spin-opposite, range-separated double-hybrid functionals optimized for excited states. As the molecule twists, the oscillator strength for S0-S1 transitions decreases while ESA shifts to shorter wavelengths. Excitation from S0 to S1 has substantial π-π* character in the ground-state conformation but becomes almost entirely a charge-transfer transition as S1 relaxes, accounting for the loss of oscillator strength. The need for solvent rearrangement explains the sensitivity of the relaxation dynamics to viscosity and temperature.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838672","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 learning the order-disorder Jahn-Teller transition in LaMnO3. LaMnO3中有序-无序jann - teller跃迁的机器学习。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0328174

Lorenzo Celiberti, Alexander Ehrentraut, Luca Leoni, Cesare Franchini

{"title":"Machine learning the order-disorder Jahn-Teller transition in LaMnO3.","authors":"Lorenzo Celiberti, Alexander Ehrentraut, Luca Leoni, Cesare Franchini","doi":"10.1063/5.0328174","DOIUrl":"https://doi.org/10.1063/5.0328174","url":null,"abstract":"We investigate the Jahn-Teller structural phase transition in LaMnO3 at TJT ≃ 750 K using molecular dynamics simulations based on machine-learning force fields trained on ab initio data. Analysis of the site-site correlation function of the distortions reveals that the transition is driven by the ordering of the Q2 Jahn-Teller distortion of the MnO6 octahedra, which acts as the order parameter and establishes the order-disorder nature of the transition. Dynamical local distortions are found to persist above TJT. Our results reproduce the experimental temperature dependence of both structural and phonon properties and highlight the presence of anharmonic effects at finite temperature. More broadly, the combined use of machine-learning molecular dynamics and velocity autocorrelation function analysis provides a robust framework for uncovering the microscopic mechanisms of structural phase transitions in correlated materials. In particular, this approach enables a clear distinction between order-disorder transitions and alternative mechanisms, such as displacive behavior, through the temperature evolution of vibrational properties.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838599","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

Eigen-microstate condensation and critical phenomena in the Lennard-Jones fluid. Lennard-Jones流体的特征-微观状态凝聚和临界现象。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0297847

Lan Yang, Zhaorong Pang, Chongzhi Qiao, Gaoke Hu, Jiaqi Dong, Rui Shi, Xiaosong Chen

{"title":"Eigen-microstate condensation and critical phenomena in the Lennard-Jones fluid.","authors":"Lan Yang, Zhaorong Pang, Chongzhi Qiao, Gaoke Hu, Jiaqi Dong, Rui Shi, Xiaosong Chen","doi":"10.1063/5.0297847","DOIUrl":"https://doi.org/10.1063/5.0297847","url":null,"abstract":"Despite extensive study of the liquid-vapor phase transition, accurately determining the critical point and the critical exponents in fluid systems through direct simulation remains a challenge. We employ the eigen-microstate theory (EMT) to investigate the liquid-vapor continuous phase transition in Lennard-Jones (LJ) fluid within the canonical ensemble. In EMT, the probability amplitudes of eigen-microstates serve as the order parameter. Using finite-size scaling of probability amplitudes, we simultaneously determine the critical temperature, Tc = 1.188(2), and critical density, ρc = 0.320(4), for an LJ potential truncated at Rc = 2.5σ. Furthermore, we obtain critical exponents of the LJ fluid, β = 0.32(2) and ν = 0.64(3), which demonstrate a great agreement with the Ising universality class. This method also reveals the mesoscopic structure of the emergent phase, characterizing the three-dimensional (3D) spatial configuration of the fluid in the critical region. This work also confirms the finite-size scaling behavior of the probability amplitudes of the eigen-microstates in the critical region. The EMT provides a powerful tool for studying the critical phenomena of complex fluid systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838616","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

A different Hubbard U value should be used for the metal-oxo cluster node in a metal-organic framework than for its extended phase: A case study of Ce-based materials. 不同的Hubbard U值应该用于金属有机框架中的金属-氧簇节点，而不是用于其扩展阶段：ce基材料的案例研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0331562

Jia Wang, Xin-Ping Wu

{"title":"A different Hubbard U value should be used for the metal-oxo cluster node in a metal-organic framework than for its extended phase: A case study of Ce-based materials.","authors":"Jia Wang, Xin-Ping Wu","doi":"10.1063/5.0331562","DOIUrl":"https://doi.org/10.1063/5.0331562","url":null,"abstract":"The Hubbard U for a metal-oxo unit depends on how electrons are screened in its host material. This screening is governed by (i) local screening determined by coordination, oxidation state, and metal-ligand hybridization and (ii) the longer-range dielectric response of the surrounding lattice. Consequently, the common practice of directly transferring U from extended metal oxides to metal-organic frameworks (MOFs) with the same metal-oxo unit risks systematic errors. Here, we take UiO-66(Ce) as a prototypical MOF and determine the node-specific linear-response Hubbard parameter U (ULR) for four commonly employed GGA functionals used to describe the Ce 4f orbitals of the Ce6O8 node. We then benchmark GGA + ULR against experiment and HSE06 for both pristine and the node-reduced UiO-66(Ce). GGA + ULR reproduces the structural and electronic properties, whereas using the U value transferred from CeO2 leads to a deviated description of the redox activity. However, transferring node-specific ULR between MOFs that share the same node and comparable screening environments is physically justified and practically useful for GGA + U calculations of large-cell MOFs. This conditional transferability is validated by applying the ULR derived from UiO-66(Ce) to NU-1000(Ce), successfully reproducing hybrid-functional results across seven proton topologies. The larger ULR obtained for the Ce6O8 node compared to that for CeO2 reflects more ionic Ce-O bonding and distinct redox chemistry of the MOF node. Such deviations are not limited to the present case but are anticipated for metal-oxo units in MOFs more broadly, enabling node chemistries that are different from those of the extended phase.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838640","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

Renormalization group approach to second-order Green's function theory. 二阶格林函数理论的重整化群方法。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0321278

Joshua Krieger, Johannes Tölle

引用次数: 0

Stable memory kernel coupling theory for quantum dynamics: Projection-based and continued fraction methods. 量子动力学的稳定记忆核耦合理论：基于投影和连分数方法。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0327266

Wei Liu, Rui-Hao Bi, Yu Su, Limin Xu, Zhennan Zhou, Yao Wang, Wenjie Dou

引用次数: 0

Cooperative chemical reactions in optical cavities: A complex interplay of mode hybridization, timescale balance, and pathway interference. 光学腔中的协同化学反应：模式杂化、时标平衡和通路干涉的复杂相互作用。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0324649

Yaling Ke

{"title":"Cooperative chemical reactions in optical cavities: A complex interplay of mode hybridization, timescale balance, and pathway interference.","authors":"Yaling Ke","doi":"10.1063/5.0324649","DOIUrl":"https://doi.org/10.1063/5.0324649","url":null,"abstract":"Harnessing strong light-matter interactions to control chemical reactions in confined electromagnetic fields offers a promising route toward deepening our understanding of chemical dynamics at the collective quantum-mechanical level, with potential implications for future chemical synthesis paradigms. Achieving this goal, however, requires an in-depth mechanistic understanding of underlying dynamical processes. As a step in this direction, we present a systematic and numerically exact quantum dynamical study of cooperative reaction dynamics inside an optical microcavity. Using a hierarchy of model systems with increasing complexity, we elucidate how cavity-modified reactivity emerges from-and is highly sensitive to-subtle structural and environmental variations. Our models consist of optically dark reactive molecules, each represented by a symmetric double well potential, coupled to infrared-active non-reactive intramolecular or solvent vibrational modes, as well as their respective dissipative environments. Our results demonstrate that cavity-induced rate modifications arise from a delicate interplay among mode hybridization in strong-coupling regimes, the dynamical balance of all participating energy exchange processes, and quantum interference between multiple fluctuation-dissipation-mediated reaction pathways enabled by collective cavity coupling. By continuously tuning a single system parameter or introducing molecular collectivity, we observe qualitatively distinct rate modification profiles as functions of the cavity frequency, including resonant rate enhancement, resonant rate suppression, hybridization-induced peak splitting, and, notably, asymmetric Fano-type line shapes in which enhancement peaks and suppression dips coexist within a narrow resonance window, highlighting the important role of quantum interference in cavity-modified chemical reactivity.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"164 17","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147838506","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

Electrostatic forces for monovalent colloids in low and high salt solutions. 低盐和高盐溶液中单价胶体的静电力。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2026-05-07 DOI: 10.1063/5.0326013

Sidi Mohammed Abdelatif Khtir, Hanene Zahaf, Hocine Alla, Manuel G Velarde

引用次数: 0