arXiv subjects

Yan Levin

Publications and source records attributed to Yan Levin.

At least 73 records · Page 4Linked to original sources

arXiv2012

Polarizable Surfaces: Weak and Strong Coupling Regimes

We study the ionic distribution near a charged surface. A new method for performing Monte Carlo simulations in this geometry is discussed. A theory is then presented that allows us to accurately reproduce the density profiles obtained in the simulations. In the weak-coupling regime, a theory accounts for the ion-image interactions, leading to a modified Poisson-Boltzmann equation. When the correlations between the ions are significant, a strong-coupling theory is used to calculate the density profiles near the surface and a Poisson-Boltzmann equation with a renormalized boundary condition to account for the counterion distribution in the far-field.

physics.chem-ph↗

arXiv2012

A close look into the excluded volume effects within a double layer

We explore the effect of steric interaction on the ionic density distribution near a charged hard wall. For weakly charged walls, small particles, and monovalent ions the mean-field Poisson-Boltzmann equation provides an excellent description of the density profiles. For large ions and large surface charges, however, deviations appear. To explore these, we use the density functional theory. We find that local density functionals are not able to account for steric interactions near a wall. Based on the weighted density approximation we derive a simple analytical expression for the contact electrostatic potential which allows us to analytically calculate the differential capacitance of the double layer.

cond-mat.soft↗

arXiv2012

Equation of state of charged colloidal suspensions and its dependence on the thermodynamic route

The thermodynamic properties of highly charged colloidal suspensions in contact with a salt reservoir are investigated in the framework of the Renormalized Jellium Model (RJM). It is found that the equation of state is very sensitive to the particular thermodynamic route used to obtain it. Specifically, the osmotic pressure calculated within the RJM using the contact value theorem can be very different from the pressure calculated using the Kirkwood-Buff fluctuation relations. On the other hand, Monte Carlo (MC) simulations show that both the effective pair potentials and the correlation functions are accurately predicted by the RJM. It is suggested that the lack of self-consistency in the thermodynamics of the RJM is a result of neglected electrostatic correlations between the counterions and coions.

cond-mat.soft↗

arXiv2012

Ion fluxes through nano-pores and transmembrane channels

We introduce an implicit solvent Molecular Dynamics approach for calculating ionic fluxes through narrow nano-pores and transmembrane channels. The method relies on a dual-control- volume grand-canonical molecular dynamics (DCV-GCMD) simulation and the analytical solution for the electrostatic potential inside a cylindrical nano-pore recently obtained by Levin [Europhys. Lett., 76, 163 (2006)]. The theory is used to calculate the ionic fluxes through an artificial trans-membrane c hannel which mimics the antibacterial gramicidin A channel. Both current-voltage and current-concentration relations are calculated under various experimental conditions. We show that our results are comparable to the characteristics associated to the gramicidin A pore, specially the existence of two binding sites inside the pore and the observed saturation in the current-concentration profiles.

cond-mat.soft↗

arXiv2012

Ergodicity Breaking and Parametric Resonances in Systems with Long-Range Interactions

We explore the mechanism responsible for the ergodicity breaking in systems with long-range forces. In thermodynamic limit such systems do not evolve to the Boltzmann-Gibbs equilibrium, but become trapped in an out-of-equilibrium quasi-stationary-state. Nevertheless, we show that if the initial distribution satisfies a specific constraint - a generalized virial condition - the quasi- stationary-state is very close to ergodic and can be described by Lynden-Bell statistics. On the other hand if the generalized virial condition is violated, parametric resonances are excited, leading to chaos and ergodicity breaking.

cond-mat.stat-mech↗

arXiv2011

Weak and Strong Coupling Theories for Polarizable Colloids and Nano-Particles

A theory is presented which allows us to accurately calculate the density profile of monovalent and multivalent counterions in suspensions of polarizable colloids or nano-particles. In the case of monovalent ions, we derive a weak-coupling theory that explicitly accounts for the ion-image interaction, leading to a modified Poisson-Boltzmann equation. For suspensions with multivalent counterions, a strong-coupling theory is used to calculate the density profile near the colloidal surface and a Poisson-Boltzmann equation with a renormalized boundary condition to account for the counterion distribution in the far-field. All the results are compared with the Monte Carlo simulations, showing an excellent agreement between the theory and the simulations.

cond-mat.soft↗

arXiv2011

Statistical Mechanics of 1d Self-Gravitating Systems: The Core-Halo Distribution

We study, using both theory and simulations, a system of self-gravitating sheets. A new statistical mechanics theory - free of any adjustable parameters - is derived to quantitatively predict the final stationary state achieved by this system after the process of collisionless relaxation is completed. The theory shows a very good agreement with the numerical simulations. The model sheds new light on the general mechanism of relaxation of self-gravitating systems and may help us to understand cold matter distribution in the Universe.

astro-ph.GA↗

arXiv2011

Core-halo distribution in the Hamiltonian Mean-Field Model

We study a paradigmatic system with long-range interactions: the Hamiltonian Mean-Field Model (HMF). It is shown that in the thermodynamic limit this model does not relax to the usual equilibrium Maxwell-Boltzmann distribution. Instead, the final stationary state has a peculiar core-halo structure. In the thermodynamic limit, HMF is neither ergodic nor mixing. Nevertheless, we find that using dynamical properties of Hamiltonian systems, it is possible to quantitatively predict both the spin distribution and the velocity distribution functions in the final stationary state, without any adjustable parameters. We also show that HMF undergoes a non-equilibrium first-order phase transition between paramagnetic and ferromagnetic states.

cond-mat.stat-mech↗

arXiv2011

Effects of the dielectric discontinuity on the counterion distribution in a colloidal suspension

We introduce a new method for simulating colloidal suspensions with spherical colloidal particles of dielectric constant different from the surrounding medium. The method uses exact calculation of the Green function to obtain the ion-ion interaction potential in the presence of a dielectric discontinuity at the surface of the colloidal particle. The new method is orders of magnitude faster than the traditional approaches based on series expansions of the interaction potential.

physics.chem-ph↗

arXiv2011

Rejoinder on: Thermostatistics of Overdamped Motion of Interacting Particles

In their Reply [arXiv:1104.5036] to our Comment [arXiv:1104.0697] Andrade et al. state that we have "chosen to categorically dismiss their elaborate and solid conceptual approach without employing any concepts or tools from Statistical Mechanics". Because of the one page restriction imposed by PRL, we could not address all of the flaws of the original paper. Therefore, we are grateful to Andrade et al., for giving us an opportunity to further elaborate on our Comment. In this Rejoinder we show that the model studied by Andrade et al. has nothing to do with the Tsallis entropy either at T=0 or at any other temperature.

cond-mat.stat-mech↗

arXiv2011

Ion specificity and the theory of stability of colloidal suspensions

A theory is presented which allow us to accurately calculate the critical coagulation concentration (CCC) of hydrophobic colloidal suspensions. For positively charged particles the CCC's follow the Hofmeister (lyotropic) series. For negatively charged particles the series is reversed. We find that strongly polarizable chaotropic anions are driven towards the colloidal surface by electrostatic and hydrophobic forces. Within approximately one ionic radius from the surface, the chaotropic anions loose part of their hydration sheath and become strongly adsorbed. The kosmotropic anions, on the other hand, are repelled from the hydrophobic surface. The theory is quantitatively accurate without any adjustable parameters. We speculate that the same mechanism is responsible for the Hofmeister series that governs stability of protein solutions.

cond-mat.soft↗

arXiv2011

Comment on: Thermostatistics of Overdamped Motion of Interacting Particles [arXiv:1008.1421]

In a recent paper, Phys. Rev. Lett. 105 260601 (2010) [arXiv:1008.1421], Andrade et al., argued that classical particles confined in a parabolic trap at T=0 distribute themselves in accordance with the Tsallis statistics. To prove their point the authors performed molecular dynamics simulations. Here we show that the model of Andrade et al. can be solved exactly. The distribution of particles at T=0 has nothing to do with the Tsallis entropy and is determined simply by the force balance.

cond-mat.stat-mech↗

arXiv2011

New ordered phases in a class of generalized XY models

It is well known that the 2D XY model exhibits an unusual infinite order phase transition belonging to the Kosterlitz-Thouless (KT) universality class. Introduction of a nematic coupling into the XY Hamiltonian leads to an additional phase transition in the Ising universality class [D.H. Lee and G. Grinstein, Phys. Rev. Lett. 55, 541 (1985)]. Using a combination of extensive Monte Carlo simulations and finite size scaling, we show that the higher order harmonics lead to a qualitatively different phase diagram, with additional ordered phases originating from the competition between the ferromagnetic and pseudonematic couplings. The new phase transitions belong to the 2D Potts, Ising, or KT universality classes.

cond-mat.stat-mech↗

arXiv2010

The renormalized Jellium model of colloidal suspensions with multivalent counterions

An extension of the renormalized Jellium model which allows to study colloidal suspensions containing trivalent counterions is proposed. The theory is based on a modified Poisson-Boltzmann equation which incorporates the effects of counterion correlations near the colloidal surfaces using a new boundary condition. The renormalized charges, the counterion density profiles, and osmotic pressures can be easily calculated using the modified renormalized Jellium model. The results are compared with the ones obtained using the traditional Wigner-Seitz (WS) cell approximation also with a new boundary condition. We find that while the thermodynamic functions obtained within the renormalized Jellium model are in a good agreement with their WS counterpart, the effective charges predicted by the two theories can be significantly different.

cond-mat.soft↗

arXiv2010

Surface tensions and surface potentials of acid solutions

A theory is presented which allows us to quantitatively calculate the excess surface tension of acid solutions. The H^+, in the form of hydronium ion, is found to be strongly adsorbed to the solution-air interface. To account for the electrostatic potential difference measured experimentally, it is necessary to assume that the hydronium ion is oriented with its hydrogens pointing into the bulk water. The theory is quantitatively accurate for surface tensions and is qualitative for electrostatic potential difference across the air-water interface.

cond-mat.soft↗

arXiv2010

Statistical Mechanics of Unbound Two Dimensional Self-Gravitating Systems

We study, using both theory and molecular dynamics simulations, the relaxation dynamics of a microcanonical two dimensional self-gravitating system. After a sufficiently large time, a gravitational cluster of N particles relaxes to the Maxwell-Boltzmann distribution. The time to reach the thermodynamic equilibrium, however, scales with the number of particles. In the thermodynamic limit, $N\to\infty$ at fixed total mass, equilibrium state is never reached and the system becomes trapped in a non-ergodic stationary state. An analytical theory is presented which allows us to quantitatively described this final stationary state, without any adjustable parameters.

cond-mat.stat-mech↗

arXiv2010

Surface tensions, surface potentials and the Hofmeister series of electrolyte solutions

A theory is presented which allows us to accurately calculate the surface tensions and the surface potentials of electrolyte solutions. Both the ionic hydration and the polarizability are taken into account. We find a good correlation between the Jones-Dole viscosity $B$-coefficient and the ionic hydration near the air-water interface. The kosmotropic anions such as fluoride, iodate, sulfate and carbonate, are found to be strongly hydrated and are repelled from the interface. The chaotropic anions such as perchlorate, iodide, chlorate and bromide are found to be significantly adsorbed to the interface. Chloride and bromate anions become weakly hydrated in the interfacial region. The sequence of surface tensions and surface potentials is found to follow the Hofmeister ordering. The theory, with only one adjustable parameter, quantitatively accounts for the surface tensions of 10 sodium salts for which there is experimental data.

cond-mat.soft↗

arXiv2009

Ions at the air-water interface: An end to one hundred year old mystery?

Availability of highly reactive halogen ions at the surface of aerosols has tremendous implications for the atmospheric chemistry. Yet neither simulations, experiments, nor existing theories are able to provide a fully consistent description of the electrolyte-air interface. In this paper a new theory is proposed which allows us to explicitly calculate the ionic density profiles, the surface tension, and the electrostatic potential difference across the solution-air interface. Predictions of the theory are compared to experiments and are found to be in excellent agreement. The theory also sheds new light on one of the oldest puzzles of physical chemistry -- the Hofmeister effect.

cond-mat.soft↗