Quasichemical theory and the description of associating fluids relative to a reference: Multiple bonding of a single site solute

We derive an expression for the chemical potential of an associating solute in a solvent relative to the value in a reference fluid using the quasichemical organization of the potential distribution theorem. The fraction of times the solute is not associated with the solvent, the monomer fraction, is expressed in terms of (a) the statistics of occupancy of the solvent around the solute in the reference fluid and (b) the Widom factors that arise because of turning on solute-solvent association. Assuming pair-additivity, we expand the Widom factor into a product of Mayer f-functions and the resulting expression is rearranged to reveal a form of the monomer fraction that is analogous to that used within the statistical associating fluid theory (SAFT). The present formulation avoids all graph-theoretic arguments and provides a fresh, more intuitive, perspective on Wertheim's theory and SAFT. Importantly, multi-body effects are transparently incorporated into the very foundations of the theory. We illustrate the generality of the present approach by considering examples of multiple solvent association to a colloid solute with bonding domains that range from a small patch on the sphere, a Janus particle, and a solute whose entire surface is available for association

Mini-grand canonical ensemble: chemical potential in the solvation shell

Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells' around solutes cannot be described within the macroscopic grand canonical framework using a single chemical potential that represents the solvent `bath'. In this communication, we hypothesize that molecular-sized observation volumes such as solvation shells are best described by coupling the solvation shell with a mixture of particle baths each with its own chemical potential. We confirm our hypotheses by studying the enhanced fluctuations in the occupancy statistics of hard sphere solvent particles around a distinguished hard sphere solute particle. Connections with established theories of solvation are also discussed

Experimental observation of chimera and cluster states in a minimal globally coupled network

A "chimera state" is a dynamical pattern that occurs in a network of coupled identical oscillators when the symmetry of the oscillator population is broken into synchronous and asynchronous parts. We report the experimental observation of chimera and cluster states in a network of four globally coupled chaotic opto-electronic oscillators. This is the minimal network that can support chimera states, and our study provides new insight into the fundamental mechanisms underlying their formation. We use a unified approach to determine the stability of all the observed partially synchronous patterns, highlighting the close relationship between chimera and cluster states as belonging to the broader phenomenon of partial synchronization. Our approach is general in terms of network size and connectivity. We also find that chimera states often appear in regions of multistability between global, cluster, and desynchronized states

Structure and thermodynamics of a mixture of patchy and spherical colloids: a multi-body association theory with complete reference fluid information

A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures. Because of multi-body correlations predicting the structure and thermodynamics of such systems remains a challenge. Earlier Marshall and Chapman developed a theory wherein association effects due to interactions multiply the partition function for clustering of particles in a reference hard-sphere system. The multi-body effects are incorporated in the clustering process, which in their work was obtained in the absence of the bulk medium. The bulk solvent effects were then modeled approximately within a second order perturbation approach. However, their approach is inadequate at high densities and for large association strengths. Based on the idea that the clustering of solvent in a defined coordination volume around the solute is related to occupancy statistics in that defined coordination volume, we develop an approach to incorporate the complete information about hard-sphere clustering in a bulk solvent at the density of interest. The occupancy probabilities are obtained from enhanced sampling simulations but we also develop a concise parametric form to model these probabilities using the quasichemical theory of solutions. We show that incorporating the complete reference information results in an approach that can predict the bonding state and thermodynamics of the colloidal solute for a wide range of system conditions.Comment: arXiv admin note: text overlap with arXiv:1601.0438

Large-scale exact diagonalizations reveal low-momentum scales of nuclei

Ab initio methods aim to solve the nuclear many-body problem with controlled approximations. Virtually exact numerical solutions for realistic interactions can only be obtained for certain special cases such as few-nucleon systems. Here we extend the reach of exact diagonalization methods to handle model spaces with dimension exceeding $10^{10}$ on a single compute node. This allows us to perform no-core shell model (NCSM) calculations for 6Li in model spaces up to $N_\mathrm{max} = 22$ and to reveal the 4He+d halo structure of this nucleus. Still, the use of a finite harmonic-oscillator basis implies truncations in both infrared (IR) and ultraviolet (UV) length scales. These truncations impose finite-size corrections on observables computed in this basis. We perform IR extrapolations of energies and radii computed in the NCSM and with the coupled-cluster method at several fixed UV cutoffs. It is shown that this strategy enables information gain also from data that is not fully UV converged. IR extrapolations improve the accuracy of relevant bound-state observables for a range of UV cutoffs, thus making them profitable tools. We relate the momentum scale that governs the exponential IR convergence to the threshold energy for the first open decay channel. Using large-scale NCSM calculations we numerically verify this small-momentum scale of finite nuclei.Comment: Minor revisions.Accepted for publication in Physical Review

A modified proximity approach in the fusion of heavy-ions

By using a suitable set of the surface energy coefficient, nuclear radius, and universal function, the original proximity potential 1977 is modified. The overestimate of the data by 4 % reported in the literature is significantly reduced. Our modified proximity potential reproduces the experimental data nicely compared to its older versions.Comment: 9 pages, 5 figures, Chin. Phys. lett.(2010) in pres

Voltage modulated electro-luminescence spectroscopy and negative capacitance - the role of sub-bandgap states in light emitting devices

Voltage modulated electroluminescence spectra and low frequency ({\leq} 100 kHz) impedance characteristics of electroluminescent diodes are studied. Voltage modulated light emission tracks the onset of observed negative capacitance at a forward bias level for each modulation frequency. Active participation of sub-bandgap defect states in minority carrier recombination dynamics is sought to explain the results. Negative capacitance is understood as a necessary dielectric response to compensate any irreversible transient changes in the minority carrier reservoir due to radiative recombinations mediated by slowly responding sub-bandgap defects. Experimentally measured variations of the in-phase component of modulated electroluminescence spectra with forward bias levels and modulation frequencies support the dynamic influence of these states in the radiative recombination process. Predominant negative sign of the in-phase component of voltage modulated electroluminescence signal further confirms the bi-molecular nature of light emission. We also discuss how these states can actually affect the net density of minority carriers available for radiative recombination. Results indicate that these sub-bandgap states can suppress external quantum efficiency of such devices under high frequency operation commonly used in optical communication.Comment: 21 pages, 4 sets of figure

Local Guarantees in Graph Cuts and Clustering

Correlation Clustering is an elegant model that captures fundamental graph cut problems such as Min $s-t$ Cut, Multiway Cut, and Multicut, extensively studied in combinatorial optimization. Here, we are given a graph with edges labeled $+$ or $-$ and the goal is to produce a clustering that agrees with the labels as much as possible: $+$ edges within clusters and $-$ edges across clusters. The classical approach towards Correlation Clustering (and other graph cut problems) is to optimize a global objective. We depart from this and study local objectives: minimizing the maximum number of disagreements for edges incident on a single node, and the analogous max min agreements objective. This naturally gives rise to a family of basic min-max graph cut problems. A prototypical representative is Min Max $s-t$ Cut: find an $s-t$ cut minimizing the largest number of cut edges incident on any node. We present the following results: $(1)$ an $O(\sqrt{n})$-approximation for the problem of minimizing the maximum total weight of disagreement edges incident on any node (thus providing the first known approximation for the above family of min-max graph cut problems), $(2)$ a remarkably simple $7$-approximation for minimizing local disagreements in complete graphs (improving upon the previous best known approximation of $48$), and $(3)$ a $1/(2+\varepsilon)$-approximation for maximizing the minimum total weight of agreement edges incident on any node, hence improving upon the $1/(4+\varepsilon)$-approximation that follows from the study of approximate pure Nash equilibria in cut and party affiliation games