Long-range electrostatic interactions between like-charged colloids: steric and confinement effects

Within the framework of a Modified Poisson-Boltzmann theory accounting for steric effects of microions, we prove analytically that the effective pair interactions between like-charge colloids immersed in a confined electrolyte are repulsive. Our approach encompasses and extends previously known results to the case of complete confinement, and further incorporates the finite size of the microions which is absent in the standard Poisson-Boltzmann theory.Comment: 5 pages, 1 figure, to appear in Physical Review

Sine-Gordon theory for the equation of state of classical hard-core Coulomb systems. II. High-temperature expansion

We perform a high-temperature expansion of the grand potential of the restrictive primitive model of electrolytes in the frame of the extended sine-Gordon theory exposed in the companion paper. We recover a result already obtained by Stell an Lebowitz (J. Chem. Phys., 49, 3706 (1968)) by means of diagrammatic expansions

On geometric aspects of diffuse groups

Bowditch introduced the notion of diffuse groups as a geometric variation of the unique product property. We elaborate on various examples and non-examples, keeping the geometric point of view from Bowditch's paper. In particular, we discuss fundamental groups of flat and hyperbolic manifolds. The appendix settles an open question by providing an example of a group which is diffuse but not left-orderable.Comment: 37 pages, main text by Kionke and Raimbault, appendix by Dunfield. v2 : updated ancillary files and added url to the reference

Using Gaussian Process Regression to Simulate the Vibrational Raman Spectra of Molecular Crystals

Vibrational properties of molecular crystals are constantly used as structural fingerprints, in order to identify both the chemical nature and the structural arrangement of molecules. The simulation of these properties is typically very costly, especially when dealing with response properties of materials to e.g. electric fields, which require a good description of the perturbed electronic density. In this work, we use Gaussian process regression (GPR) to predict the static polarizability and dielectric susceptibility of molecules and molecular crystals. We combine this framework with ab initio molecular dynamics to predict their anharmonic vibrational Raman spectra. We stress the importance of data representation, symmetry, and locality, by comparing the performance of different flavors of GPR. In particular, we show the advantages of using a recently developed symmetry-adapted version of GPR. As an examplary application, we choose Paracetamol as an isolated molecule and in different crystal forms. We obtain accurate vibrational Raman spectra in all cases with fewer than 1000 training points, and obtain improvements when using a GPR trained on the molecular monomer as a baseline for the crystal GPR models. Finally, we show that our methodology is transferable across polymorphic forms: we can train the model on data for one structure, and still be able to accurately predict the spectrum for a second polymorph. This procedure provides an independent route to access electronic structure properties when performing force-evaluations on empirical force-fields or machine-learned potential energy surfaces