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Register a new userInterplay of local hydrogen-bonding and long-ranged dipolar forces in simulations of confined water
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Spherical truncations of Coulomb interactions in standard models for water permit efficient molecular simulations and can give remarkably accurate results for the structure of the uniform liquid. However truncations are known to produce significant errors in nonuniform systems, particularly for electrostatic properties. Local molecular field (LMF) theory corrects such truncations by use of an effective or restructured electrostatic potential that accounts for effects of the remaining long-ranged interactions through a density-weighted mean field average and satisfies a modified Poissons equation defined with a Gaussian-smoothed charge density. We apply LMF theory to three simple molecular systems that exhibit different aspects of the failure of a naive application of spherical truncations -- water confined between hydrophobic walls, water confined between atomically-corrugated hydrophilic walls, and water confined between hydrophobic walls with an applied electric field. Spherical truncations of 1/r fail spectacularly for the final system in particular, and LMF theory corrects the failings for all three. Further, LMF theory provides a more intuitive way to understand the balance between local hydrogen bonding and longer-ranged electrostatics in molecular simulations involving water.
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Using general scaling arguments combined with mean-field theory we investigate the critical ($T simeq T_c$) and off-critical ($T e T_c$) behavior of the Casimir forces in fluid films of thickness $L$ governed by dispersion forces and exposed to long-ranged substrate potentials which are taken to be equal on both sides of the film. We study the resulting effective force acting on the confining substrates as a function of $T$ and of the chemical potential $mu$. We find that the total force is attractive both below and above $T_c$. If, however, the direct substrate-substrate contribution is subtracted, the force is repulsive everywhere except near the bulk critical point $(T_c,mu_c)$, where critical density fluctuations arise, or except at low temperatures and $(L/a) (betaDelta mu) =O(1)$, with $Delta mu=mu-mu_c <0$ and $a$ the characteristic distance between the molecules of the fluid, i.e., in the capillary condensation regime. While near the critical point the maximal amplitude of the attractive force if of order of $L^{-d}$ in the capillary condensation regime the force is much stronger with maximal amplitude decaying as $L^{-1}$. Essential deviations from the standard finite-size scaling behavior are observed within the finite-size critical region $L/xi=O(1)$ for films with thicknesses $L lesssim L_{rm crit}$, where $L_{rm crit}=xi_0^pm (16 |s|)^{ u/beta}$, with $ u$ and $beta$ as the standard bulk critical exponents and with $s=O(1)$ as the dimensionless parameter that characterizes the relative strength of the long-ranged tail of the substrate-fluid over the fluid-fluid interaction. We present the modified finite-size scaling pertinent for such a case and analyze in detail the finite-size behavior in this region.
In this paper, we compute exactly the average density of a harmonically confined Riesz gas of $N$ particles for large $N$ in the presence of a hard wall. In this Riesz gas, the particles repel each other via a pairwise interaction that behaves as $|x_i - x_j|^{-k}$ for $k>-2$, with $x_i$ denoting the position of the $i^{rm th}$ particle. This density can be classified into three different regimes of $k$. For $k geq 1$, where the interactions are effectively short-ranged, the appropriately scaled density has a finite support over $[-l_k(w),w]$ where $w$ is the scaled position of the wall. While the density vanishes at the left edge of the support, it approaches a nonzero constant at the right edge $w$. For $-1<k<1$, where the interactions are weakly long-ranged, we find that the scaled density is again supported over $[-l_k(w),w]$. While it still vanishes at the left edge of the support, it diverges at the right edge $w$ algebraically with an exponent $(k-1)/2$. For $-2<k< -1$, the interactions are strongly long-ranged that leads to a rather exotic density profile with an extended bulk part and a delta-peak at the wall, separated by a hole in between. Exactly at $k=-1$ the hole disappears. For $-2<k< -1$, we find an interesting first-order phase transition when the scaled position of the wall decreases through a critical value $w=w^*(k)$. For $w<w^*(k)$, the density is a pure delta-peak located at the wall. The amplitude of the delta-peak plays the role of an order parameter which jumps to the value $1$ as $w$ is decreased through $w^*(k)$. Our analytical results are in very good agreement with our Monte-Carlo simulations.
We show that spherical truncations of the 1/r interactions in models for water and acetonitrile yield very accurate results in bulk simulations for all site-site pair correlation functions as well as dipole-dipole correlation functions. This good performance in bulk simulations contrasts with the generally poor results found with the use of such truncations in nonuniform molecular systems. We argue that Local Molecular Field (LMF) theory provides a general theoretical framework that gives the necessary corrections to simple truncations in most nonuniform environments and explains the accuracy of spherical truncations in uniform environments by showing that these corrections are very small. LMF theory is derived from the exact Yvon-Born-Green (YBG) hierarchy by making physically-motivated and well-founded approximations. New and technically interesting derivations of both the YBG hierarchy and LMF theory for a variety of site-site molecular models are presented in appendices. The main paper focuses on understanding the accuracy of these spherical truncations in uniform systems both phenomenologically and quantitatively using LMF theory.
We study the dynamical behavior of a square lattice Ising model with exchange and dipolar interactions by means of Monte Carlo simulations. After a sudden quench to low temperatures we find that the system may undergo a coarsening process where stripe phases with different orientations compete or alternatively it can relax initially to a metastable nematic phase and then decay to the equilibrium stripe phase through nucleation. We measure the distribution of equilibration times for both processes and compute their relative probability of occurrence as a function of temperature and system size. This peculiar relaxation mechanism is due to the strong metastability of the nematic phase, which goes deep in the low temperature stripe phase. We also measure quasi-equilibrium autocorrelations in a wide range of temperatures. They show a distinct decay to a plateau that we identify as due to a finite fraction of frozen spins in the nematic phase. We find indications that the plateau is a finite size effect. Relaxation times as a function of temperature in the metastable region show super-Arrhenius behavior, suggesting a possible glassy behavior of the system at low temperatures.
The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments.
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