Hard-core Interactions Research Articles

One dimensional lattice fluid mixture with nearest neighbour interactions

We present an exact derivation of the free energy functional of a fluid mixture of hard rods with arbitrary sizes on a one-dimensional lattice. Our approach is based on the Wertheim cluster theory which consists of mapping a system with finite range interactions to the system with pure hard-core interaction but with modified activities. We show that the free energy functional has the same form as the fundamental measure functional. The interactions part of the free energy has two contributions, one from the one-particle cavity restricted to the hard rod or hard-sphere diameter and a second from the two-particle cavity which includes the finite range of the interaction. In the limit of a one-component system, our results reduce to the one derived using the Markov chain approach. For vanishing interactions, the density functionals coincide exactly with the previously derived for the mixture of hard rods with pure hard-core interaction.

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 an essential tool for understanding the structure, dynamics, and phase behavior of 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 parametrize 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 × 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 boundaries.

Influence of catastrophes and hidden dynamical symmetries on ultrafast backscattered photoelectrons

We discuss the effect of using potentials with a Coulomb tail and different degrees of softening in photoelectron momentum distributions (PMDs) using the recently implemented hybrid forward-boundary CQSFA (H-CQSFA). We show that introducing a softening in the Coulomb interaction influences the ridges observed in the PMDs associated with backscattered electron trajectories. In the limit of a hard-core Coulomb interaction, the rescattering ridges close along the polarization axis, while for a soft-core potential, they are interrupted at ridge-specific angles. We analyze the momentum mapping of the different orbits leading to the ridges. For the hard-core potential, there exist two types of saddle-point solutions that coalesce at the ridge. By increasing the softening, we show that two additional solutions emerge as the result of breaking a hidden dynamical symmetry associated exclusively with the Coulomb potential. Further signatures of this symmetry breaking are encountered in subsets of momentum-space trajectories. Finally, we use scattering theory to show how the softening affects the maximal scattering angle and provide estimates that agree with our observations from the CQSFA. This implies that, in the presence of residual binding potentials in the electron's continuum propagation, the distinction between purely kinematic and dynamic caustics becomes blurred. Published by the American Physical Society 2024

Gibbs measures for fertile models with hard-core interactions and four states

Gibbs measures for fertile models with hard-core interactions and four states

Systematic Incorporation of Ionic Hard-Core Size into the Debye-Hückel Theory via the Cumulant Expansion of the Schwinger-Dyson Equations.

The Debye-Hückel (DH) formalism of bulk electrolytes equivalent to the Gaussian-level closure of the electrostatic Schwinger-Dyson identities without the interionic hard-core (HC) coupling is extended via the cumulant treatment of these equations augmented by HC interactions. By comparing the monovalent ion activity and pressure predictions of our cumulant-corrected DH (CCDH) theory with hypernetted-chain results and Monte Carlo simulations from the literature, we show that this rectification extends the accuracy of the DH formalism from submolar to molar salt concentrations. In the case of internal energies or the general case of divalent electrolytes mainly governed by charge correlations, the improved accuracy of the CCDH theory is limited to submolar ion concentrations. Comparison with experimental data from the literature shows that, via the adjustment of the hydrated ion radii, CCDH formalism can equally reproduce the nonuniform effect of salt increment on the ionic activity coefficients up to molar concentrations. The inequality satisfied by these HC sizes coincides with the cationic branch of the Hofmeister series.

Understanding the glassy dynamics from melting temperatures in binary glass-forming liquids.

It is natural to expect that small particles in binary mixtures move faster than large ones. However, in binary glass-forming liquids with soft-core particle interactions, we observe the counterintuitive dynamic reversal between large and small particles along with the increase of pressure by performing molecular dynamics simulations. The structural relaxation (dynamic heterogeneity) of small particles is faster (weaker) than large ones at low pressures, but becomes slower (stronger) above a crossover pressure. In contrast, this dynamic reversal never happens in glass-forming liquids with hard-core interactions. We find that the difference of the effective melting temperatures felt by large and small particles can be used to understand the dynamic reversal. In binary mixtures, we derive effective melting temperatures of large and small particles simply from the conversion of units and find that particles with a higher effective melting temperature usually undergo a slower and more heterogeneous relaxation. The presence (absence) of the dynamic reversal in soft-core (hard-core) systems is simply due to the non-monotonic (monotonic) behavior of the melting temperature as a function of pressure. Interestingly, by manipulating the relative softness between large and small particles, we obtain a special case of soft-core systems, in which large particles always have higher effective melting temperatures than small ones. As a result, the dynamic reversal is totally eliminated. Our work provides another piece of evidence of the underlying connections between the properties of non-equilibrium glass-formers and equilibrium crystal-formers.

Phase transitions in systems of particles with only hard-core interactions

This article contains our comments and views on the status of the current understanding of phase transitions in systems in thermodynamic equilibrium with only hard-core interactions, based on our work in this area. The equation of state for the hard sphere gas in d-dimensions is discussed. The universal repulsive Lee-Yang singularity in the complex activity plane, and its relation to the directed and undirected polymer models are outlined. We also discuss orientationally disordered crystalline mesophases, and some of their models.

Current fluctuations in an interacting active lattice gas

We study the fluctuations of the integrated density current across the origin up to time T in a lattice model of active particles with hard-core interactions. This model is amenable to an exact description within a fluctuating hydrodynamics framework. We focus on quenched initial conditions for both the density and the magnetization fields and derive expressions for the cumulants of the density current, which can be matched with direct numerical simulations of the microscopic lattice model. For the case of uniform initial profiles, we show that the variance of the integrated current displays three regimes: an initial rise with a coefficient given by the symmetric simple exclusion process, a cross-over regime where the effects of activity increase the fluctuations, and a large-time behavior with a prefactor that depends on the initial conditions, the Péclet number, and the mean density of particles. Additionally, we study the limit of zero diffusion, where the fluctuations intriguingly exhibit a T 2 behavior at short times. However, at large times, the fluctuations still grow as , with a coefficient that can be calculated explicitly. For low densities, we show that this coefficient can be expressed in terms of the effective diffusion constant D eff for non-interacting active particles.

Uphill in Reaction-Diffusion Multi-species Interacting Particles Systems

We study reaction-diffusion processes with multi-species particles and hard-core interaction. We add boundary driving to the system by means of external reservoirs which inject and remove particles, thus creating stationary currents. We consider the condition that the time evolution of the average occupation evolves as the discretized version of a system of coupled diffusive equations with linear reactions. In particular, we identify a specific one-parameter family of such linear reaction-diffusion systems where the hydrodynamic limit behaviour can obtained by means of a dual process. We show that partial uphill diffusion is possible for the discrete particle systems on the lattice, whereas it is lost in the hydrodynamic limit.

Tensor network construction for lattice gas models: Hard-core and triangular lattice models.

The representation of complex lattice models in the form of a tensor network is a promising approach to the analysis of the thermodynamics of such systems. Once the tensor network is built, various methods can be used to calculate the partition function of the corresponding model. However, it is possible to build the initial tensor network in different ways for the same model. In this work, we have proposed two ways of constructing tensor networks and demonstrated that the construction process affects the accuracy of calculations. For demonstration purposes, we have done a brief study of the 4 nearest-neighbor (NN) and 5NN models, where adsorbed particles exclude all sites up to the fourth and fifth nearest neighbors from being occupied by another particle. In addition, we have studied a 4NN model with finite repulsions with a fifth neighbor. In a sense, this model is intermediate between 4NN and 5NN models, so algorithms designed for systems with hard-core interactions may experience difficulties. We have obtained adsorption isotherms, as well as graphs of entropy and heat capacity for all models. The critical values of the chemical potential were determined from the position of the heat capacity peaks. As a result, we were able to improve our previous estimate of the position of the phase transition points for the 4NN and 5NN models. And in the model with finite interactions, we found the presence of two first-order phase transitions and made an estimate of the critical values of the chemical potential for them.

Interfacial microstructure of neutral and charged polymer brushes: A density functional theory study.

Polymer density functional theory (PDFT) is a computationally efficient and robust statistical mechanics theory for capturing the interfacial microstructure of grafted polymer brushes (PBs). Undoubtedly, the intramolecular and intermolecular interactions in PDFT (e.g., hard-core interactions and direct Coulomb interactions) are greatly affected by the grafting behavior of PBs. However, the combination of these interactions with the physical constraints on grafting behavior remains unclear and there is a remarkable difference in the density profile of grafted PB between PDFT and simulation. Herein, we propose a PDFT to study neutral and charged grafted PBs by incorporating the physical constraints of end-grafted PBs into the excess free energies due to intramolecular and intermolecular interactions. This PDFT has been successfully validated where the density distributions of neutral and weakly charged PBs predicted by the PDFT are in excellent agreement with the results of the Monte Carlo and molecular dynamics simulations. In addition, the significant contribution of grafting behavior to the free energy of PB systems is presented. Consequently, this work provides a powerful and accurate theoretical method to reveal the interfacial microstructure of grafted PBs.

The energy of dilute Bose gases II: the general case

For a dilute system of non-relativistic bosons in 3 dimensions interacting through a positive, radially symmetric, potential v with scattering length a we prove that the ground state energy density satisfies the bound \(e(\rho ) \ge 4\pi a \rho ^2 (1+ \frac{128}{15\sqrt{\pi }} \sqrt{\rho a^3} +o(\sqrt{\rho a^3}\,))\), thereby proving a lower bound consistent with the Lee–Huang–Yang formula for the energy density. The proof allows for potentials with large \(L^1\)-norm, in particular, the case of hard core interactions is included. Thereby, we solve a problem in mathematical physics that had been a major challenge since the 1950’s.

Structural correlations and phase separation in binary mixtures of charged and neutral colloids.

Structural correlations between colloids in a binary mixture of charged and neutral spheres are calculated using computer simulations of the primitive model with explicit microions. For aqueous suspensions in a solvent of large dielectric constant, the traditional Derjaguin-Landau-Vervey-Overbeek (DLVO) theory of linear screening, supplemented with hard core interactions, reproduces the structural correlations obtained in the full primitive model quantitatively. However, for lower dielectric contrast, the increasing Coulomb coupling between the counterions and charged colloids results in strong deviations. We find a fluid-fluid phase separation into two regions either rich in charged or rich in neutral colloids, which is not reproduced by DLVO theory. Our results are verifiable in scattering or real-space experiments on charged-neutral mixtures of colloids or nanoparticles.

Thermodynamics of Interacting Hard Rods on a Lattice

We present an exact derivation of the isobaric partition function of lattice hard rods with arbitrary nearest neighbor interactions. Free energy and all thermodynamics functions are derived accordingly and they written in a form that is a suitable for numerical implementation. As an application, we have considered lattice rods with pure hard core interactions, rods with long range gravitational attraction and finally a charged hard rods with charged boundaries (Bose gas), a model that is relevant for studying several phenomena such as charge regulation, ionic liquids near charged interfaces, and an array of charged smectic layers or lipid multilayers. In all cases, thermodynamic analysis have been done numerically using the Broyden algorithm.

The primitive model in classical density functional theory: beyond the standard mean-field approximation

The primitive model describes ions by point charges with an additional hard-core interaction. In classical density-functional theory (DFT) the mean-field electrostatic contribution can be obtained from the first order of a functional perturbation of the pair potential for an uncharged reference system of hard spheres. This mean-field electrostatic term particularly contributes at particle separations that are forbidden due to hard-core overlap. In this work we modify the mean-field contribution such that the pair potential is constant for distances smaller than the contact distance of the ions. We motivate our modification by the underlying splitting of the potential, which is similar to the splitting of the Weeks–Chandler–Andersen potential and leads to higher-order terms in the respective expansion of the functional around the reference system. The resulting formalism involves weighted densities similar to the ones found in fundamental measure theory. To test our modifications, we analyze and compare density profiles, direct and total correlation functions, and the thermodynamic consistency of the functional via a widely established sum rule and the virial pressure formula for our modified functional, for established functionals, and for data from computer simulations. We found that our modifications clearly show improvements compared to the standard mean-field functional, especially when predicting layering effects and direct correlation functions in high concentration scenarios; for the latter we also find improved consistency when calculated via different thermodynamic routes. In conclusion, we demonstrate how modifications toward higher order corrections beyond mean-field functionals can be made and how they perform, by this providing a basis for systematic future improvements in classical DFT for the description of electrostatic interactions.

Macromolecular Crowding Is More than Hard-Core Repulsions.

Cells are crowded, but proteins are almost always studied in dilute aqueous buffer. We review the experimental evidence that crowding affects the equilibrium thermodynamics of protein stability and protein association and discuss the theories employed to explain these observations. In doing so, we highlight differences between synthetic polymers and biologically relevant crowders. Theories based on hard-core interactions predict only crowding-induced entropic stabilization. However, experiment-based efforts conducted under physiologically relevant conditions show that crowding can destabilize proteins and their complexes. Furthermore, quantification of the temperature dependence of crowding effects produced by both large and small cosolutes, including osmolytes, sugars, synthetic polymers, and proteins, reveals enthalpic effects that stabilize or destabilize proteins.Crowding-induced destabilization and the enthalpic component point to the role of chemical interactions between and among the macromolecules, cosolutes, and water. We conclude with suggestions for future studies.

Microscopic Theory for the Diffusion of an Active Particle in a Crowded Environment.

We calculate the diffusion coefficient of an active tracer in a schematic crowded environment, represented as a lattice gas of passive particles with hardcore interactions. Starting from the master equation of the problem, we put forward a closure approximation that goes beyond trivial mean field and provides the diffusion coefficient for an arbitrary density of crowders in the system. We show that our approximation is accurate for a very wide range of parameters, and that it correctly captures numerous nonequilibrium effects, which are the signature of the activity in the system. In addition to the determination of the diffusion coefficient of the tracer, our approach allows us to characterize the perturbation of the environment induced by the displacement of the active tracer. Finally, we consider the asymptotic regimes of low and high densities, in which the expression of the diffusion coefficient of the tracer becomes explicit, and which we argue to be exact.

Explicit solvent theory of salt-induced dielectric decrement

We introduce a field-theoretic electrolyte model composed of structured solvent molecules and salt ions coupled by electrostatic and hard-core (HC) interactions. Within this explicit solvent framework, we characterize the salt-driven dielectric decrement by including salt-solvent correlations beyond weak-coupling (WC) electrostatics. The WC approximation of prior formalisms is relaxed by treating the salt charges via a virial expansion. This virial approach enables the explicit inclusion of the many-body salt-solvent interactions, and directly leads to the experimentally observed linear decay of the electrolyte permittivity with added dilute salt. The permittivity formula emerging from our approach indicates that the reduction of the solvent permittivity is induced by the salt screening of the polarization charges suppressing the dielectric response of the solvent. By comparison with experiments, we also show that the salt-dressed permittivity formula can equally reproduce the attenuation of the electrolyte permittivity with rising temperature, the thermal decay of the dielectric decrement, and its intensification with the salt valency. In accordance with the observation of previous numerical simulations and implicit solvent theories, the consistent qualitative agreement of our theory with this wide range of experimental trends points out the electrostatic ion-solvent correlations as the primary mechanism behind the salt-induced dielectric decrement.

Induced surface and curvature tension equation of state for hadron resonance gas in finite volumes and its relation to morphological thermodynamics

Here, we develop an original approach to investigate the grand canonical partition function of the multicomponent mixtures of Boltzmann particles with hard-core interaction in finite and even small systems of the volumes above 20 fm3. The derived expressions of the induced surface tension equation of state (EoS) are analyzed in detail. It is shown that the metastable states, which can emerge in the finite systems with realistic interaction, appear at very high pressures at which the hadron resonance gas, most probably, is not applicable at all. It is shown how and under what conditions the obtained results for finite systems can be generalized to include into a formalism the equation for curvature tension. The applicability range of the obtained equations of induced surface and curvature tensions for finite systems is discussed and their close relations to the equations of the morphological thermodynamics are established. The hadron resonance gas model on the basis of the obtained advanced EoS is worked out. Also, this model is applied to analyze the chemical freeze-out of hadrons and light nuclei with the number of (anti-) baryons not exceeding 4. Their multiplicities were measured by the ALICE Collaboration in the central lead–lead collisions at the center-of-mass energy [Formula: see text] TeV.

Space-Resolved OH Vibrational Spectra of the Hydration Shell around CO2.

The CO2 molecule is weakly bound in water. Here we analyze the influence of a dissolved CO2 molecule on the structure and OH vibrational spectra of the surrounding water. From the analysis of ab initio molecular dynamics simulations (BLYP-D3) we present static (structure, coordination, H-bonding, tetrahedrality) and dynamical (OH vibrational spectra) properties of the water molecules as a function of distance from the solute. We find a weakly oscillatory variation (“ABBA”) in the ‘solution minus bulk water’ spectrum. The origin of these features can largely be traced back to solvent–solute hard-core interactions which lead to variations in density and tetrahedrality when moving from the solute’s vicinity out to the bulk region. The high-frequency peak in the solute-affected spectra is specifically analyzed and found to originate from both water OH groups that fulfill the geometric H-bond criteria, and from those that do not (dangling ones). Effectively, neither is hydrogen-bonded.