arXiv subjects

Zhen-Gang Wang

Publications and source records attributed to Zhen-Gang Wang.

At least 19 recordsLinked to original sources

arXiv2026

Methane and ethane adsorption on calcite surfaces: effects of surface morphology from molecular dynamics and 3D-RISM

Understanding the adsorption of alkanes on mineral surfaces is important for industrial processes such as oil and gas recovery from shale reservoirs. Previous studies have examined the adsorption of functionalized and non-functionalized alkanes on calcite, as well as adsorption under confinement. However, real surfaces commonly exhibit defects that can influence adsorption behavior. In this work, molecular dynamics (MD) simulations and the three-dimensional reference interaction site model (3D-RISM) are used to investigate the adsorption of methane and ethane on calcite surfaces with step defects. MD simulations were carried out with and without positional restraints to investigate the effects of carbonate reorientation. 3D-RISM calculations were performed on these structures and on energy-minimized configurations of the relaxed crystal. Both methods show adsorption enhanced at step defects relative to flat regions, with methane exhibiting higher excess adsorption than ethane. Carbonate reorientation at the relaxed step edges reduces the local density peaks at specific step sites in both methods, while the integrated excess adsorption from MD remains comparable to that of the restrained surface. 3D-RISM predicts lower maxima for the highest density peaks and larger excess adsorption than MD, but reproduces the spatial organization and overall adsorption trends at a fraction of the computational cost. These results highlight the importance of surface heterogeneity in fluid-mineral interactions and demonstrate that 3D-RISM is an efficient tool for semi-quantitative screening of adsorption across complex surface geometries

cond-mat.mtrl-sci↗

arXiv2026

Stockmayer Fluid with a Shifted Dipole. III. Ion Solvation

Though ion solvation is well understood for the standard Stockmayer fluid, the effect of displacing the point dipole of a Stockmayer particle, a simple geometric modification, on ion-solvent structuring and solvation thermodynamics remains less understood. We use molecular dynamics simulations to describe how a dipole shift affects radial and orientational solvent structure around centered ions, how strongly the solvent distinguishes cations and anions, and how the solvent mediates ion-ion pairing. We show that, with a centered dipole, cations and anions have equal preferences for the local solvent environment. Shifting the dipole breaks the fore-aft symmetry of the local electrostatic field, leading to a stronger preference for a Stockmayer particle's dipole to orient towards an anion and a weaker preference to orient away from a cation. These structural asymmetries propagate to the solvation free energies: increasing dipole displacement makes anion solvation more favorable, while cation solvation becomes less favorable overall across dipole strengths. The same asymmetry also manifests in the effective ion-ion interaction-increasing the dipole shift reorganizes the local solvation environment, enhancing solvent shielding of short-range cation-anion contact while weakening screening at longer range. As a result, solvent-separated configurations become comparatively more favorable, whereas increasing dipole strength produces the opposite trend. Such effects cannot be explained by bulk dielectric screening alone, indicating that molecular charge geometry plays an important role in both single-ion solvation and solvent-mediated ion-ion interactions. This work demonstrates that dipole location, not only magnitude, provides a geometric control on ion-specific solvation and ion pairing in general polar fluids.

cond-mat.stat-mech↗

arXiv2026

Microphase Separation and Ionic Aggregation in Oppositely Charged End-Functionalized Polymer Blends

We study the phase behavior of binary blends of polymers with oppositely charged termini using an ion-correlation-augmented self-consistent field theory (IC-SCFT). Under the low dielectric conditions typical for organic polymer melts, strong ion correlations drive association of multiple chain ends, leading to emergent multichain architectures that go beyond a simple ion-paired diblock copolymer picture previously used to interpret recent experiments. At moderate to strong polymer segregation, the resulting phase diagram differs considerably from this effective-diblock prediction: ion clustering broadens the lamellar and cylindrical windows while suppressing the network phases, the reverse of the trend for end-charged diblock copolymers. At weak segregation, the two polymers remain miscible even as ion clustering persists, and decreasing chain length drives the clusters themselves through a sphere-to-cylinder-to-lamella shape transition, connecting continuously to the aggregation behavior of classical terminally charged ionomers in the limit when one of the polymer species shrinks to just the charged end. These results reveal that ion clustering -- beyond simple pairwise bonding -- shapes the self-assembly of end-charged polymer blends.

cond-mat.soft↗

arXiv2026

Explicit Solvents Reverse Temperature Dependence of Phase Behavior in Charged Fluids

In most theories of electrolyte and polyelectrolyte solutions, the solvent is treated implicitly as a dielectric continuum. While this approximation has enabled major advances, it neglects coupling between ionic and dipolar degrees of freedom. Using molecular dynamics simulations and the mean-spherical approximation, we show that this coupling qualitatively alters electrostatically driven phase behaviour. At finite ion concentrations, many-body ion-dipole correlations reverse the temperature dependence of effective electrostatic interactions, leading to upper-critical solution temperature (UCST) behaviour in direct contrast to the lower-critical solution temperature (LCST) behaviour predicted by implicit-solvent electrostatic theories. This phase reversal arises from ion-induced suppression of local dipolar screening, a collective effect inaccessible to pairwise implicit-solvent descriptions.

cond-mat.soft↗

arXiv2026

End-Functionalized Ions Promote Stability of Highly Frustrated Phases in Diblock Copolymers

Block copolymers self-assemble into ordered nanostructures whose geometry is governed by a competition between interfacial energy and chain conformational entropy. While this competition produces a rich sequence of morphologies, topologically complex ``frustrated'' phases, such as the primitive cubic network and single networks, incur severe packing penalties and are difficult to access in neutral systems. Here we show that ions functionalized at the termini of one block in an AB diblock copolymer melt introduce a qualitatively new stabilization mechanism. Strong ion correlations drive chain-end association and generate a curvature preference toward the charged domain; the resulting tendency of end-localized ion clusters to adopt compact, curved geometries selectively favors the highly frustrated single-primitive-cubic network ($Pm\bar{3}m$) and single-gyroid network ($I$4$_1$32) over the classical phases, in a region of parameter space with a segregation strength lying below the order-disorder transition of the neutral system. Free energy decomposition reveals that the electrostatic energy, arising almost entirely from beyond-mean-field ion correlations, becomes increasingly negative with increasing interfacial curvature. In the primitive cubic network, pronounced local segregation of ions into the cylindrical struts generates compact curved clusters whose correlation energy gain more than offsets the enhanced packing frustration, so the very geometry that is the source of packing frustration in neutral systems becomes the source of its stability here. Increasing ion size weakens correlations and suppresses the network phases, consistent with experimental observations. Our results establish curvature-selective end-group association as a general principle for accessing frustrated topologies in block copolymer systems.

cond-mat.soft↗

arXiv2026

How Topology Shapes the Phase Behavior of Polyelectrolytes

We develop a topology-specific theory of polyelectrolyte coacervation using the random phase approximation and apply it to both simple and complex coacervation. Our results for stars and dendrimers show that more compact chain topologies display a greater propensity for liquid-liquid phase separation, as a function of both Bjerrum length and salt concentration. For mixtures of different topologies, we demonstrate that differences in polymer topology alone are sufficient to drive multiphase coacervation of polyelectrolytes, which we rationalize in terms of an effective $χ$ parameter. Analysis of a simplified global phase diagram reveals that the propensity for such topology-driven phase separation is largest at a finite molecular weight. Overall, our results establish polymer topology as a powerful design lever for tuning the phase diagram of charged macromolecules independently of molecular weight, net charge, and monomer chemistry, since changes in topology enable fine-tuning of the effective charge density without altering these molecular characteristics.

cond-mat.soft↗

arXiv2026

Stockmayer Fluid with a Shifted Dipole: Bulk Behavior

Shifting the point dipole from the center of a Stockmayer particle is a simple geometric modification that has been explored previously, yet its implications for liquid structure, dielectric response, and phase behavior remain incompletely understood. Here, we combine molecular dynamics simulations with analytical theory to provide a unified physical interpretation of how dipole displacement reshapes microscopic correlations and propagates to macroscopic thermodynamic properties. We show that dipole shifting breaks the fore-aft symmetry of the local electrostatic field, producing only modest changes in radial packing but strong alterations in angular structure within the first solvation shell. Enhanced alignment near the dipole head is accompanied by frustrated orientational correlations near the tail, leading to broader angular distributions and a shift away from axial configurations at strong coupling. These structural asymmetries weaken cooperative ordering and result in a systematic reduction of the dielectric constant, despite locally stronger interactions. For large shifts, the dielectric response approaches the Debye limit, indicating effective suppression of dipole-dipole correlations. The same geometric frustration governs vapor-liquid equilibria: while increasing dipole strength raises the critical temperature, even modest shifts disrupt the highly polarized liquid states that emerge at strong coupling and can suppress ferroelectric-like ordering. Predictions from a reparameterized COFFEE theory capture these trends within its domain of validity, highlighting the direct connection between local orientational structure and macroscopic observables. Overall, this work demonstrates that dipole location, not only magnitude, provides a powerful control parameter in dipolar fluids and offers a clear framework for understanding geometric frustration in electrostatic liquids.

cond-mat.soft↗

arXiv2026

Device-independent quantum key distribution over 100 km with single atoms

Device-independent quantum key distribution (DI-QKD) is a key application of the quantum internet. We report the realization of DI-QKD between two single-atom nodes linked by 100-km fibers. To improve the entangling rate, single-photon interference is leveraged for entanglement heralding, and quantum frequency conversion is used to reduce fiber loss. A tailored Rydberg-based emission scheme suppresses the photon recoil effect on the atom without introducing noise. We achieved high-fidelity atom-atom entanglement and positive asymptotic key rates for fiber lengths up to 100 km. At 11 km, 1.2 million heralded Bell pairs were prepared over 624 hours, yielding an estimated extractable finite-size secure key rate of 0.112 bits per event against general attacks. Our results close the gap between proof-of-principle quantum network experiments and real-world applications.

quant-ph↗

arXiv2025

Mechanisms of Chain Exchange in Diblock Copolymer Micelles

We investigate the mechanism of chain exchange in diblock copolymer micelles using two distinct yet complementary simulation techniques. First, enhanced sampling method is combined with coarse-grained molecular dynamics to compute a two-dimensional free energy surface for the chain expulsion process in the strong segregation regime. To facilitate chain expulsion, a distance-based collective variable is biased, and the end-to-end distance of the core block is also biased to ensure sufficient sampling of chain conformations. The free energy surface reveals a bimodal distribution of chain conformations along the effective reaction coordinate. The minimum free energy pathway qualitatively aligns with the Halperin-Alexander budding-like mechanism. The free energy barrier along this pathway is calculated for core block lengths ranging from $N_\textrm{core}=4$-$100$, and the barrier is shown to scale as $βΔF_\textrm{barr} \sim N_\textrm{core}^{2/3}$, consistent with the Halperin-Alexander prediction for a globular transition state. Notably, the free energy surface also reveals a nearly degenerate alternative pathway in which the chain escapes by extending out bead-by-bead, in agreement with previous simulations. We also study the case of a dense copolymer melt, where the core-block shrinks but does not collapse into a dry compact globule in the opposite phase. To examine the kinetic pathway, a simplified model is introduced in which a single chain escapes from a planar interface within a mean-field background. Forward flux sampling calculations yield a linear scaling of the barrier, $βΔF_\textrm{barr} \sim N_\textrm{core}$, in agreement with experimental observations and prior simulations. Moreover, analysis of successful escape trajectories highlights an extended chain conformation at the transition state.

cond-mat.soft↗

arXiv2025

Stockmayer Fluid with a Shifted Dipole: Interfacial Behavior

We investigate the properties of the liquid-vapor interface in the shifted Stockmayer fluid using molecular dynamics simulations in the canonical ensemble. We study the role of the dipole moment strength and the degree of asymmmetry on equilibrium interfacial characteristics, including density profiles, polar order, nematic order, interfacial polarization, electric field, and electrostatic potential. In addition, we compute angular distribution functions across the interface to gain insight into how the dipole shift affects the molecular orientation. We find that the shift significantly effects angular distribution functions by altering the polar order while leaving the nematic order relatively unaffected, in comparison to the reference symmetric Stockmayer fluid. We find that these results are consistently explained using an image-dipole construction that has been previously applied to symmetric Stockmayer fluids but has never been extended to the shifted model. We find remarkable agreement between the simple theory and the simulations in the qualitative shape of the distribution functions for both the liquid and vapor phases in proximity to the interface. Unexpectedly, the spontaneous polarization at the interface, and therefore the generated electric field, changes sign as the dipole moment strength increases. This also leads to an inversion of the sign of the potential difference across the interface.

cond-mat.soft↗

arXiv2024

Hydrodynamics in Semidilute Polyelectrolyte Solutions and Complex Coacervates

It is generally assumed that hydrodynamics in dense polyelectrolyte (PE) solutions, such as semidilute PE solutions and PE complex coacervates, is heavily screened and inconsequential. Here, using mesoscale molecular dynamics that explicitly accounts for hydrodynamics, we show that segmental dynamics in the subdiffusive regime show strong signatures of hydrodynamic interactions that persist well beyond the correlation length of semidilute PE solutions with moderately short chains. The strong hydrodynamic effects are also observed in coacervate systems containing moderately short chains, even with PE concentration as high as $30\%$. Our work fills a gap in the existing simulation literature on dense PE solutions and hints at the importance of hydrodynamics in the transport and rheological properties in broader polymer/polyelectrolyte solution systems.

cond-mat.soft↗

arXiv2024

Image charge effects under metal and dieletric boundary conditions

Image charge effect is a fundamental problem in electrostatics. However, a proper treatment at the continuum level for many-ion systems, such as electrolyte solutions or ionic liquids, remains an open theoretical question. Here, we demonstrate and systematically compare the image charge effects under metal and dielectric boundary conditions (BCs), based on a renormalized Gaussian-fluctuation theory. Our calculations for a simple 1:1 symmetric electrolyte in the point-charge approximation show that the double-layer structure, capacitance, and interaction forces between like-charged plates depend strongly on the types of boundaries, even in the weak-coupling regime. Like-charge attraction is predicted for both metal and dielectric BCs. Finally, we comment on the effects of a dielectrically-saturated solvent layer on the metal surface. We provide these results to serve as a baseline for comparison with more realistic molecular dynamics simulations and experiments.

cond-mat.soft↗

arXiv2024

GCMe: Efficient implementation of the Gaussian core model with smeared electrostatic interactions for molecular dynamics simulations of soft matter systems

In recent years, molecular dynamics (MD) simulations have emerged as a pivotal tool for understanding the structure, dynamics, and phase behavior in charged soft matter systems. To explore phenomena across greater length and time scales in MD simulations, molecules are often coarse-grained for better computational performance. However, commonly-used force fields represent particles as hard-core interaction centers with point charges, which often overemphasizes the packing effect and short-range electrostatics, especially in systems with bulky deformable organic molecules and systems with strong coarse-graining. This underscores the need for an efficient soft-core model to physically capture the effective interactions between coarse-grained particles. To this end, we implement a soft-core model uniting the Gaussian core model with smeared electrostatic interactions that is phenomenologically equivalent to recent theoretical models. We first parameterize it generically using water as the model solvent. Then, we benchmark its performance in the OpenMM toolkit for different boundary conditions to highlight a computational speedup of up to $34\times$ compared to commonly used force fields and existing implementations. Finally, we demonstrate its utility by investigating how boundary polarizability affects the adsorption behavior of a polyelectrolyte solution on perfectly conducting and nonmetal electrodes.

physics.comp-ph↗

arXiv2023

Ion Conductivity in Salt-Doped Polymers: Combined Effects of Temperature and Salt Concentration

We construct a coarse-grained molecular dynamics model based on poly(ethylene oxide) and lithium bis-(trifluoromethane)sulfonimide salt to examine the combined effects of temperature and salt concentration on the transport properties. Salt doping notably slows down the dynamics of polymer chains and reduces ion diffusivity, resulting in a glass transition temperature increase proportional to the salt concentration. The polymer diffusion is shown to be well represented by a modified Vogel-Fulcher-Tamman (M-VFT) equation that accounts for both the temperature and salt concentration dependence. Furthermore, we find that at any temperature, the concentration dependence of the conductivity is well described by the product of its infinite dilution value and a correction factor accounting for the reduced segmental mobility with increasing salt concentration. These results highlight the important role of polymer segmental mobility in the salt concentration dependence of ionic conductivity for temperatures near and above the glass transition.

cond-mat.soft↗

arXiv2023

Adsorption isotherm and mechanism of $\mathrm{Ca^{2+}}$ binding to polyelectrolyte

Polyelectrolytes, such as polyacrylic acid (PAA), can effectively mitigate $\mathrm{CaCO_3}$ scale formation. Despite their success as antiscalants, the underlying mechanism of $\mathrm{Ca^{2+}}$ binding to polyelectrolyte chains remains unresolved. Through all-atom molecular dynamics simulations, we construct an adsorption isotherm of $\mathrm{Ca^{2+}}$ binding to sodium polyacrylate ($\mathrm{NaPAA}$) and investigate the associated binding mechanism. We find that the number of calcium ions adsorbed $[\mathrm{Ca^{2+}_{ads}}]$ to the polymer saturates at moderately high concentrations of free calcium ions $[\mathrm{Ca^{2+}_{aq}}]$ in the solution. This saturation value is intricately connected with the binding modes accessible to $\mathrm{Ca^{2+}}$ ions when they bind to the polyelectrolyte chain. We identify two dominant binding modes: the first involves binding to at most two carboxylate oxygens on a polyacrylate chain, and the second, termed the high binding mode, involves binding to four or more carboxylate oxygens. As the concentration of free calcium ions $[\mathrm{Ca^{2+}_{aq}}]$ increases from low to moderate levels, the polyelectrolyte chain undergoes a conformational transition from an extended coil to a hairpin-like structure, enhancing the accessibility to the high binding mode. At moderate concentrations of $[\mathrm{Ca^{2+}_{aq}}]$, the high binding mode accounts for at least a third of all binding events. The chain's conformational change and its consequent access to the high binding mode is found to increase the overall $\mathrm{Ca^{2+}}$ ion binding capacity of the polyelectrolyte chain.

cond-mat.soft↗

arXiv2023

Multi-valent Ion Mediated Polyelectrolyte Association and Structure

Polyelectrolytes are commonly used to chelate multi-valent ions in aqueous solutions, playing a critical role in water softening and the prevention of mineralization. At sufficient ionic strength, ion-mediated polyelectrolyte--polyelectrolyte interactions can precipitate polyelectrolyte--ion complexes, a phenomenon known as "like-charge attraction". While the significant influence of small ions on polyelectrolyte solution phase behavior is recognized, the precise molecular mechanisms driving the counterintuitive phenomenon remain largely elusive. In this study, we employ all-atom molecular dynamics simulations to investigate the molecular mechanism of like-charge attraction between two poly(acrylic acid) (PAA) chains in solution. We find that moderate quantities of Ca$^{2+}$ ions induce attraction between PAA chains, facilitated by the formation of PAA--Ca$^{2+}$--PAA bridges and a significant increase in the coordination of Ca$^{2+}$ ions by the PAA chains. At high Ca$^{2+}$ number densities, ion bridges are disfavored due to electrostatic screening, yet the chains are still attracted to each other due to solvent-mediated interactions between the chains and their chelated ions. The insights gleaned from this study not only enrich our understanding of the intricate mechanism of like-charge attraction between polyanions in solution but also illuminate the influence of multi-valent ions on polyelectrolyte interactions.

cond-mat.soft↗

arXiv2023

Charge Asymmetry Suppresses Coarsening Dynamics in Polyelectrolyte Complex Coacervation

Mixing solutions of oppositely charged macromolecules can result in liquid-liquid phase separation into a polymer-rich coacervate phase and a polymer-poor supernatant phase. Here we show that charge asymmetry in the constituent polymers can slow down the coarsening dynamics, with an apparent growth exponent that deviates from the well-known 1/3 for neutral systems and decreases with increasing degrees of charge asymmetry. Decreasing solvent quality accelerates the coarsening dynamics for asymmetric mixtures, but slows down the coarsening dynamics for symmetric mixtures. We rationalize these results by examining the interaction potential between merging droplets.

cond-mat.soft↗

arXiv2022

Topological Forces in a Model System for Reptation Dynamics

We construct a micromechanical version of an early model for topologically constrained polymers -- a 2D chain amongst point-like uncrossable obstacles -- which allows us to explicitly elucidate the role of topological forces beyond confining the chain to a curvilinear tube-like path. Our simulations reveal that linear relaxation of the contour length \textit{along the tube} is slowed down by the presence of topological forces that can be considered as additional effective topological ``friction'' in quiescence. However, this perspective fails in predicting the strong forces that resist the imposed curvilinear motion of the chain during nonlinear startup microrheology. These entropic forces are nonlocal in nature and result from an unexpected coupling between orientational and longitudinal dynamics.

cond-mat.soft↗