Journal of Chemical Physics最新文献_第5页

Role of quantum corrections to the kinetic energy and three-body interactions on the thermodynamic properties of neon. 动能和三体相互作用的量子修正对氖热力学性质的作用。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-28 DOI: 10.1063/5.0272013

Ulrich K Deiters, Richard J Sadus

引用次数: 0

Kinetics of phase transition in nonreciprocal mixtures of passive and chemophoretically active particles. 被动和化学反应活性粒子非互易混合物的相变动力学。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0258020

Manisha Jhajhria, Subir K Das, Snigdha Thakur

{"title":"Kinetics of phase transition in nonreciprocal mixtures of passive and chemophoretically active particles.","authors":"Manisha Jhajhria, Subir K Das, Snigdha Thakur","doi":"10.1063/5.0258020","DOIUrl":"https://doi.org/10.1063/5.0258020","url":null,"abstract":"We study phase separation kinetics in two-dimensional binary mixtures of active and passive colloids. An active particle acts as a source of the chemical gradient to induce phoretic motion among the passive particles. Mediated by this effective interaction, the suspension undergoes separation resembling a vapor-liquid phase transition. Via simulations incorporating Langevin dynamics, we construct the related steady-state phase diagram. We exploit this knowledge to study structure and growth associated with kinetics following sudden quenches of homogeneous systems into the miscibility gap, for far-from-critical and near-critical densities. An advanced finite-size scaling technique is employed to calculate the growth exponents in the thermodynamically large system size limit, using data from systems of different finite sizes, for each of the cases. The growth data are described well by a recently constructed analytical function, irrespective of system size and particle density. Our results demonstrate enhancement in the growth exponent when the phoretic strength is increased. For the off-critical case, we have discussed the possible mechanism(s) in the background of an appropriate theoretical picture.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144110974","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

Triply bonded C≡C characteristics between planar hypercoordinate carbons in a two-dimensional Be4C3 monolayer. 三键C≡二维Be4C3单层中平面超配碳之间的C特征。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0264650

Rui Bian, Zheng-Xuan Wang, Meng-Hui Wang, Zhong-Hua Cui

{"title":"Triply bonded C≡C characteristics between planar hypercoordinate carbons in a two-dimensional Be4C3 monolayer.","authors":"Rui Bian, Zheng-Xuan Wang, Meng-Hui Wang, Zhong-Hua Cui","doi":"10.1063/5.0264650","DOIUrl":"https://doi.org/10.1063/5.0264650","url":null,"abstract":"We report the discovery of two 2D Be4C3 monolayers-o-Be4C3 and m-Be4C3-as the lowest-energy structures, each exhibiting unique planar hypercoordinate carbon bonding characteristics. Both monolayers feature a C≡C triply bonded motif formed between planar tetracoordinate carbon (ptC) and planar pentacoordinate carbon (ppC) centers, coordinating with three Be atoms in o-Be4C3 and four Be atoms in m-Be4C3. Bonding analysis reveals dual behavior: the p-orbital electrons in the C≡C bonds remain primarily localized, while other ptC atoms coordinated with four Be atoms exhibit fully delocalized electron density across the Be4C framework. This mainly localized π-bonding makes Be4C3 the first 2D material to feature multiply bonded planar hypercoordinate carbon motifs. Both monolayers demonstrate good thermodynamic and kinetic stability. Notably, o-Be4C3 possesses a small indirect bandgap, while m-Be4C3 exhibits 2D phonon-mediated superconductivity with a transition temperature (Tc) of 4.5 K, connecting \"anti-van't Hoff/Le Bel\" structures to promising applications in electronics and optoelectronics.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093912","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

From internal state variables to fluctuations in glass-forming materials: The linear dynamic heat capacity, expansivity, and compressibility. 从内部状态变量到玻璃成形材料的波动：线性动态热容量、膨胀率和可压缩性。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0259276

Claudio Corbisieri

{"title":"From internal state variables to fluctuations in glass-forming materials: The linear dynamic heat capacity, expansivity, and compressibility.","authors":"Claudio Corbisieri","doi":"10.1063/5.0259276","DOIUrl":"https://doi.org/10.1063/5.0259276","url":null,"abstract":"Several macroscopic-phenomenological theories exist that account for dissipative effects in the dynamic behavior of glass-forming materials. Thermodynamics with internal state variables, for example, provides a rationale for assessing the multiplicity of relaxation mechanisms observed in the linear dynamic heat capacity, expansivity, and compressibility. However, the convoluted formalism of these theories often obstructs the assessment of microscopic characteristics associated with material behavior that can otherwise be studied within linear response theory. In this work, we address this problem by deriving memory functionals of the entropy and volume from a set of ordinary differential equations posed by the normal-coordinate transform of the internal state variables. A generalized susceptibility matrix that represents the linear dynamic material behavior in the frequency domain is the result. In agreement with microscopic reversibility, the generalized susceptibility matrix and its time-domain transform are symmetric, thus substantiating the hypothesis of equal distribution of relaxation times in pressure-jump entropy relaxation and temperature-jump volume relaxation. The Prigogine-Defay ratio in terms of equilibrium fluctuations is obtained from the imaginary part of the generalized susceptibility matrix via the fluctuation-dissipation theorem. By combining fundamentals from classical irreversible thermodynamics and rational thermodynamics to derive the memory functionals, this work contributes to a theoretical framework for assessing macroscopic-phenomenological and microscopic characteristics of glass-forming materials associated with the linear dynamic heat capacity, expansivity, and compressibility. In addition, a compilation of the generalized susceptibility and its time-domain transform, both evaluated for the relaxation-time distributions that lead to the Debye, Kohlrausch, Cole-Cole, Davidson-Cole, and Havriliak-Negami relaxation functions, is provided.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093821","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

Quantitative relations between nearest-neighbor persistence and slow heterogeneous dynamics in supercooled liquids. 过冷液体中最近邻持久性与慢非均质动力学的定量关系。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0262404

Katrianna S Sarkar, Kevin A Interiano-Alberto, Jack F Douglas, Robert S Hoy

{"title":"Quantitative relations between nearest-neighbor persistence and slow heterogeneous dynamics in supercooled liquids.","authors":"Katrianna S Sarkar, Kevin A Interiano-Alberto, Jack F Douglas, Robert S Hoy","doi":"10.1063/5.0262404","DOIUrl":"https://doi.org/10.1063/5.0262404","url":null,"abstract":"Using molecular dynamics simulations of a binary Lennard-Jones model of glass-forming liquids, we examine how the decay of the normalized neighbor-persistence function CB(t), which decays from unity at short times to zero at long times as particles lose the neighbors that were present in their original first coordination shell, compares with those of other, more conventionally utilized relaxation metrics. In the strongly non-Arrhenius temperature regime below the onset temperature TA, we find that CB(t) can be described using the same generic double-stretched-exponential functional form that is often utilized to fit the self-intermediate scattering function S(q, t) of glass-forming liquids in this regime. The ratio of the bond lifetime τbond associated with CB(t)'s slower decay mode to the α-relaxation time τα varies appreciably and non-monotonically with T, peaking at τbond/τα ≃ 45 at T ≃ Tx, where Tx is a crossover temperature separating the high- and low-temperature regimes of glass-formation. In contrast, τbond remains on the order of the overlap time τov (the time interval over which a typical particle moves by half its diameter), and the peak time τχ for the susceptibility χB(t) associated with the spatial heterogeneity of CB(t) remains on the order of τimm (the characteristic lifetime of immobile-particle clusters), even as each of these quantities varies by roughly 5 orders of magnitude over our studied range of T. Thus, we show that CB(t) and χB(t) provide semi-quantitative spatially-averaged measures of the slow heterogeneous dynamics associated with the persistence of immobile-particle clusters.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093907","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

Theoretical modeling of adsorption isotherms and isosteric heat of associating and non-associating fluids using the two-dimensional SAFT-VR Mie approach. 基于二维SAFT-VR Mie方法的缔合和非缔合流体吸附等温线和等等热理论建模

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0263353

Andrea García-Hernández, Ana Yañez-Aulestia, Salomón Cordero-Sánchez, J Marcos Esparza-Schulz, Ilich A Ibarra, Alejandro Martínez-Borquez, Víctor M Trejos

{"title":"Theoretical modeling of adsorption isotherms and isosteric heat of associating and non-associating fluids using the two-dimensional SAFT-VR Mie approach.","authors":"Andrea García-Hernández, Ana Yañez-Aulestia, Salomón Cordero-Sánchez, J Marcos Esparza-Schulz, Ilich A Ibarra, Alejandro Martínez-Borquez, Víctor M Trejos","doi":"10.1063/5.0263353","DOIUrl":"https://doi.org/10.1063/5.0263353","url":null,"abstract":"In this work, the two-dimensional Statistical Associating Fluid Theory for fluids interacting via Mie pair potentials (2D-SAFT-VR Mie) is applied to model adsorption isotherms and isosteric heat of adsorption for both associating and non-associating fluids on solid surfaces. First, we derive analytical expressions for the first- and second-order perturbation terms of the Helmholtz free energy in the 2D system, based on the radial distribution function of a hard-disk system. Next, we develop an adsorption model that accounts for the interactions between the adsorbed and bulk phases, incorporating the Mie pair potential as a function of repulsive and attractive exponents. The theoretical approach is validated against Gibbs ensemble Monte Carlo simulations for the adsorption isotherms of associating and non-associating fluids, showing excellent agreement. Finally, the 2D-SAFT-VR Mie approach is applied to describe the adsorption isotherms and isosteric heat of adsorption of methane, nitrogen, carbon dioxide, sulfur dioxide, and water on carbonaceous materials, including dry activated carbon, zeolites, and metal-organic frameworks (MOFs). The energy depth of the surface-particle potential (ɛw) and the specific surface area (as) are free molecular parameters determined by fitting to experimental adsorption isotherms. The obtained ɛw and as values are consistent with the experimental values of isosteric heat of adsorption at zero coverage and Brunauer-Emmett-Teller surface area, respectively. In all cases, the calculated adsorption behavior exhibits excellent agreement with experimental data. These findings provide valuable theoretical insights into the design and optimization of efficient fluid storage, separation, and purification systems in complex materials.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093910","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

Microscopic theory of activated ion hopping in polymerized ionic liquids and glasses. 聚合离子液体和玻璃中活化离子跳跃的微观理论。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0262448

Ankita Das, Kenneth S Schweizer

{"title":"Microscopic theory of activated ion hopping in polymerized ionic liquids and glasses.","authors":"Ankita Das, Kenneth S Schweizer","doi":"10.1063/5.0262448","DOIUrl":"https://doi.org/10.1063/5.0262448","url":null,"abstract":"We combine polymer integral equation theory of structure with microscopic dynamical theories of activated relaxation to formulate a theory of ion hopping in supercooled polymerized ionic liquids (PolyILs) and glasses. Activation barriers and the mean ion relaxation time are analyzed as a function of the ion-to-monomer size ratio, polymer persistence length, intrachain degree of dynamic cooperativity, anion-cation Coulomb attraction strength, and dielectric constant. A general finding is the dominance of Coulomb cage correlations and anion-cation attractions in determining the hopping rate of the small ions studied. A critical finding is that the activation barrier exists only above a threshold value of the system-specific dimensionless Coulomb attraction strength. As a consequence, the barrier grows in a highly nonlinear manner with anion-cation attraction energy. This suggests a route to super-ionic transport via a relatively modest reduction of the Coulombic association energy, an effect that becomes more dramatic the smaller the mobile ion. The temperature-dependent growth of the ion relaxation time is non-Arrhenius in the supercooled liquid, but may, or may not, crossover to an apparent Arrhenius form in the glass depending on how the dielectric constant on the relevant timescale changes with temperature. The magnitude of dynamic decoupling between the ion and polymer alpha relaxation times at the laboratory glass transition, the degree of trajectory level coupling of the ion and monomer motion, and ion jump lengths are also determined. A high level discussion of the connections between theory, experiments, and simulations, and a quantitative application to specific lithium, sodium, and potassium PolyILs, are presented.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144110916","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

Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition. 氙溶剂中碘的再组合：气态团簇到液态的转变。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0260087

M Mirakhory, A Majumdar, M Ihme, A C T van Duin

{"title":"Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition.","authors":"M Mirakhory, A Majumdar, M Ihme, A C T van Duin","doi":"10.1063/5.0260087","DOIUrl":"https://doi.org/10.1063/5.0260087","url":null,"abstract":"Supercritical fluids (SCFs) have attracted significant attention as solvents for chemical reactions due to their unique properties, such as high diffusivity, low viscosity, and tunable solvation properties. These properties profoundly influence reaction kinetics and are often attributed to the formation of molecular clusters within SCFs. To study the effect of supercritical solvent on chemical reactivity and dynamics of reactions, one needs to understand the dynamics of clusters in supercritical fluid. Extensive experiments on the photodissociation and recombination of iodine in supercritical fluids served as a model system for understanding these effects. Experimental studies have been complemented by theoretical and computational investigations, which mostly employ Monte Carlo or empirical molecular dynamics simulations. However, computational studies using non-reactive force fields and ab initio approaches present challenges in capturing reactive processes at larger scales within supercritical fluids. In this work, we developed the ReaxFF parameters by training against quantum mechanics data. ReaxFF reactive force field based molecular dynamics simulations were performed, studying the dynamics of a xenon solvent and cage effect at different thermodynamic conditions for the iodine recombination reaction. We show that the conditions near the critical point are the optimal conditions to study the cage effect. We show that the average lifetime of xenon clusters ranging between 5 and 11 ps is comparable to iodine geminate recombination. Our simulation results of iodine recombination in xenon solvent demonstrate the higher probability of iodine molecule formation in the presence of xenon clusters. Finally, we show that the supercritical condition exhibits the highest recombination rate for iodine atoms.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093905","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

Singular transport in non-equilibrium strongly internal-coupled 1D tilted field spin-1/2 chain. 非平衡强内耦合一维倾斜场自旋-1/2链中的奇异输运。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0259168

Yi-Jia Yang, Yu-Qiang Liu, Zheng Liu, Chang-Shui Yu

{"title":"Singular transport in non-equilibrium strongly internal-coupled 1D tilted field spin-1/2 chain.","authors":"Yi-Jia Yang, Yu-Qiang Liu, Zheng Liu, Chang-Shui Yu","doi":"10.1063/5.0259168","DOIUrl":"https://doi.org/10.1063/5.0259168","url":null,"abstract":"Non-equilibrium spin-chain systems have been attracting increasing interest in energy transport. This work studies a one-dimensional non-equilibrium Ising chain immersed in a tilted magnetic field, where every spin contacts a Boson reservoir with the dissipative system-environment interaction. We analytically investigate the dynamics and the steady-state energy transport taking advantage of the Born-Markov-secular master equation. In the longitudinal field, one can find that the non-dissipative N' spins decompose the spin chain into N' + 1 independent subchains and block the heat currents from the hot end to the cool end. Moreover, for the non-dissipative μth spin, its nearest two bulk spins become the nodal spins in the subchains and have the corresponding energy correction of ±Jμ-1,μ and ±Jμ,μ+1 depending on the excited/ground state of the μth spin. Therefore, a magnetically controlled heat modulator can be designed by adjusting the direction of the magnetic field in which the non-dissipative spin is located. For the transverse field case, the whole Hilbert space of the chain can always be divided into two independent subspaces regardless of whether the bulk spin is dissipative. This work provides new insight into the dynamics and energy transport of the dissipative Ising model.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093908","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

Topological constraints on proton dynamics in water clusters. 水团簇中质子动力学的拓扑约束。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-05-21 DOI: 10.1063/5.0261130

Andrey M Tokmachev

{"title":"Topological constraints on proton dynamics in water clusters.","authors":"Andrey M Tokmachev","doi":"10.1063/5.0261130","DOIUrl":"https://doi.org/10.1063/5.0261130","url":null,"abstract":"Interconversion of H-bond configurations is an essential element of the water cluster dynamics. Different local mechanisms form pathways between H-bond configurations-intrabond motion of all protons in an ordered cycle of H-bonds, rotation of a pair of H-bonded water molecules, as well as the classical Grotthuss mechanism in charged clusters-resulting in extended proton rearrangement networks. An outstanding problem is whether these reaction networks are connected or fall apart into disconnected fragments to set barriers to proton dynamics. Here, the topological aspect of this problem is addressed. The network connectivity for individual mechanisms and their combinations is studied analytically using basic tools of graph theory. The connectivity is proven for wide classes of water clusters, manifesting the great power of the simple mechanisms in the interconversion of H-bond configurations. The structural motifs leading to the disintegration of proton rearrangement networks are identified. The analytical conclusions are complemented by a numerical examination of characteristic clusters. The results are relevant to studies of water-based ferroelectrics. They provide a framework for the analysis of proton dynamics in water clusters.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144093911","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