Model of a fluid at small and large length scales and the hydrophobic effect

We present a statistical field theory to describe large length scale effects induced by solutes in a cold and otherwise placid liquid. The theory divides space into a cubic grid of cells. The side length of each cell is of the order of the bulk correlation length of the bulk liquid. Large length scale states of the cells are specified with an Ising variable. Finer length scale effects are described with a Gaussian field, with mean and variance affected by both the large length scale field and by the constraints imposed by solutes. In the absence of solutes and corresponding constraints, integration over the Gaussian field yields an effective lattice gas Hamiltonian for the large length scale field. In the presence of solutes, the integration adds additional terms to this Hamiltonian. We identify these terms analytically. They can provoke large length scale effects, such as the formation of interfaces and depletion layers. We apply our theory to compute the reversible work to form a bubble in liquid water, as a function of the bubble radius. Comparison with molecular simulation results for the same function indicates that the theory is reasonably accurate. Importantly, simulating the large length scale field involves binary arithmetic only. It thus provides a computationally convenient scheme to incorporate explicit solvent dynamics and structure in simulation studies of large molecular assemblies

Eyewitnesses to the Suddenly Online Paradigm Shift in Education: Perspectives on the Experience, Sustaining Effective Teaching and Learning, and Forecasts for the Future

Introducing this special issue of the Journal of Literacy and Technology, the second part of the two-part special issues focusing on the COVID-19 “suddenly online” transition to remote/virtual eLearning modalities during the Spring of 2020. This article introduces the emergency voices from the field arising from the COVID-19 “suddenly online” transition to remote/virtual eLearning modalities during the Spring of 2020. This rare, and perhaps “once in a lifetime” momentous COVID-19 pandemic induced a paradigmatic shift in teaching and learning modalities. The first-hand eyewitness accounts which emerged from the turbulent months of the “suddenly online” transition in education are important to capture direct reports from participant observers of the experience. That in this case, many of these participant-observers are also trained educators, academic researchers, and able to provide meta-perspectives on those experiences makes recollections, reports, and perspectives even more remarkable and essential

Providing Foundations for an Educational Revolution: Moving Towards an Integrated Perspective

The pandemic of Spring 2020 necessitated a rapid switch in teaching methods around the world. Most significantly was the revolutionary transition from face to face instruction to remote, distance, or virtual teaching/learning and the resultant online “new normal” that continues to ripple across the academy and society at large. This new reality has necessitated a paradigmatic shift in how scholars, teachers and administrators understand, create, employ, and assess teaching/learning. It has likewise resulted in a shift in how students, parents, families, and employers understand, value, desire, and prefer educational formats and settings. The authors point to the importance of considering aspects of theory, research, and best practices related to this transition. The article surveys resulting first response scholarship and forecast types of questions that loom large regarding the practice of online teaching in the new economic, academic, social framework

Local Variational Principle

A generalization of the Gibbs-Bogoliubov-Feynman inequality for spinless particles is proven and then illustrated for the simple model of a symmetric double-well quartic potential. The method gives a pointwise lower bound for the finite-temperature density matrix and it can be systematically improved by the Trotter composition rule. It is also shown to produce groundstate energies better than the ones given by the Rayleigh-Ritz principle as applied to the groundstate eigenfunctions of the reference potentials. Based on this observation, it is argued that the Local Variational Principle performs better than the equivalent methods based on the centroid path idea and on the Gibbs-Bogoliubov-Feynman variational principle, especially in the range of low temperatures.Comment: 15 pages, 5 figures, one more section adde

Self Consistent Molecular Field Theory for Packing in Classical Liquids

Building on a quasi-chemical formulation of solution theory, this paper proposes a self consistent molecular field theory for packing problems in classical liquids, and tests the theoretical predictions for the excess chemical potential of the hard sphere fluid. Results are given for the self consistent molecular fields obtained, and for the probabilities of occupancy of a molecular observation volume. For this system, the excess chemical potential predicted is as accurate as the most accurate prior theories, particularly the scaled particle (Percus-Yevick compressibility) theory. It is argued that the present approach is particularly simple, and should provide a basis for a molecular-scale description of more complex solutions.Comment: 6 pages and 5 figure

Low-temperature dynamical simulation of spin-boson systems

The dynamics of spin-boson systems at very low temperatures has been studied using a real-time path-integral simulation technique which combines a stochastic Monte Carlo sampling over the quantum fluctuations with an exact treatment of the quasiclassical degrees of freedoms. To a large degree, this special technique circumvents the dynamical sign problem and allows the dynamics to be studied directly up to long real times in a numerically exact manner. This method has been applied to two important problems: (1) crossover from nonadiabatic to adiabatic behavior in electron transfer reactions, (2) the zero-temperature dynamics in the antiferromagnetic Kondo region 1/2<K<1 where K is Kondo's parameter.Comment: Phys. Rev. B (in press), 28 pages, 6 figure

A quantitative theory-versus-experiment comparison for the intense laser dissociation of H2+

A detailed theory-versus-experiment comparison is worked out for H$_2^+$ intense laser dissociation, based on angularly resolved photodissociation spectra recently recorded in H.Figger's group. As opposite to other experimental setups, it is an electric discharge (and not an optical excitation) that prepares the molecular ion, with the advantage for the theoretical approach, to neglect without lost of accuracy, the otherwise important ionization-dissociation competition. Abel transformation relates the dissociation probability starting from a single ro-vibrational state, to the probability of observing a hydrogen atom at a given pixel of the detector plate. Some statistics on initial ro-vibrational distributions, together with a spatial averaging over laser focus area, lead to photofragments kinetic spectra, with well separated peaks attributed to single vibrational levels. An excellent theory-versus-experiment agreement is reached not only for the kinetic spectra, but also for the angular distributions of fragments originating from two different vibrational levels resulting into more or less alignment. Some characteristic features can be interpreted in terms of basic mechanisms such as bond softening or vibrational trapping.Comment: submitted to PRA on 21.05.200

Charge and Current Sum Rules in Quantum Media Coupled to Radiation

This paper concerns the equilibrium bulk charge and current density correlation functions in quantum media, conductors and dielectrics, fully coupled to the radiation (the retarded regime). A sequence of static and time-dependent sum rules, which fix the values of certain moments of the charge and current density correlation functions, is obtained by using Rytov's fluctuational electrodynamics. A technique is developed to extract the classical and purely quantum-mechanical parts of these sum rules. The sum rules are critically tested in the classical limit and on the jellium model. A comparison is made with microscopic approaches to systems of particles interacting through Coulomb forces only (the non-retarded regime). In contrast with microscopic results, the current-current correlation function is found to be integrable in space, in both classical and quantum regimes.Comment: 19 pages, 1 figur

Self-assembly mechanism in colloids: perspectives from Statistical Physics

Motivated by recent experimental findings in chemical synthesis of colloidal particles, we draw an analogy between self-assembly processes occurring in biological systems (e.g. protein folding) and a new exciting possibility in the field of material science. We consider a self-assembly process whose elementary building blocks are decorated patchy colloids of various types, that spontaneously drive the system toward a unique and predetermined targeted macroscopic structure. To this aim, we discuss a simple theoretical model -- the Kern-Frenkel model -- describing a fluid of colloidal spherical particles with a pre-defined number and distribution of solvophobic and solvophilic regions on their surface. The solvophobic and solvophilic regions are described via a short-range square-well and a hard-sphere potentials, respectively. Integral equation and perturbation theories are presented to discuss structural and thermodynamical properties, with particular emphasis on the computation of the fluid-fluid (or gas-liquid) transition in the temperature-density plane. The model allows the description of both one and two attractive caps, as a function of the fraction of covered attractive surface, thus interpolating between a square-well and a hard-sphere fluid, upon changing the coverage. By comparison with Monte Carlo simulations, we assess the pros and the cons of both integral equation and perturbation theories in the present context of patchy colloids, where the computational effort for numerical simulations is rather demanding.Comment: 14 pages, 7 figures, Special issue for the SigmaPhi2011 conferenc

An optimization principle for deriving nonequilibrium statistical models of Hamiltonian dynamics

A general method for deriving closed reduced models of Hamiltonian dynamical systems is developed using techniques from optimization and statistical estimation. As in standard projection operator methods, a set of resolved variables is selected to capture the slow, macroscopic behavior of the system, and the family of quasi-equilibrium probability densities on phase space corresponding to these resolved variables is employed as a statistical model. The macroscopic dynamics of the mean resolved variables is determined by optimizing over paths of these probability densities. Specifically, a cost function is introduced that quantifies the lack-of-fit of such paths to the underlying microscopic dynamics; it is an ensemble-averaged, squared-norm of the residual that results from submitting a path of trial densities to the Liouville equation. The evolution of the macrostate is estimated by minimizing the time integral of the cost function. The value function for this optimization satisfies the associated Hamilton-Jacobi equation, and it determines the optimal relation between the statistical parameters and the irreversible fluxes of the resolved variables, thereby closing the reduced dynamics. The resulting equations for the macroscopic variables have the generic form of governing equations for nonequilibrium thermodynamics, and they furnish a rational extension of the classical equations of linear irreversible thermodynamics beyond the near-equilibrium regime. In particular, the value function is a thermodynamic potential that extends the classical dissipation function and supplies the nonlinear relation between thermodynamics forces and fluxes