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Patrick Charbonneau

Patrick Charbonneau contributes to research discovery and scholarly infrastructure.

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Published work

15 published item(s)

preprint2026arXiv

The critical slowing down in diffusion models

Computational sampling has been central to the sciences since the mid-20th century. While machine-learning-based approaches have recently enabled major advances, their behavior remains poorly understood, with limited theoretical control over when and why they succeed. Here we provide such insight for diffusion models-a class of generative schemes highly effective in practice-by analyzing their application to the $O(n)$ model of statistical field theory in the Gaussian limit $n \to \infty$. In this analytically tractable setting, we show that training a score model with a one-layer network architecture matching the exact solution exhibits a form of critical slowing down in parameter learning. This slowing down also impacts the generation process, indicating that the well-known difficulties of sampling near criticality persist even for learned generative models. To overcome this bottleneck, we demonstrate the power of combining architectural depth with physical locality. We find that using a two-layer architecture drastically reduces the critical slowing down, with the training time scaling logarithmically rather than quadratically with system size. By introducing a local score approximation we show that this acceleration in training time can be achieved without increasing the number of neural network parameters. Taken together, these results demonstrate that diffusion models can overcome the critical slowing down through appropriate architectural design, and establish a controlled framework for understanding and improving learned sampling methods in statistical physics and beyond.

preprint2022arXiv

Equilibrium Fluctuations in Mean-field Disordered Models

Mean-field models of glasses that present a random first order transition exhibit highly non-trivial fluctuations. Building on previous studies that focused on the critical scaling regime, we here obtain a fully quantitative framework for all equilibrium conditions. By means of the replica method we evaluate Gaussian fluctuations of the overlaps around the thermodynamic limit, decomposing them in thermal fluctuations inside each state and heterogeneous fluctuations between different states. We first test and compare our analytical results with numerical simulation results for the p-spin spherical model and the random orthogonal model, and then analyze the random Lorentz gas. In all cases, a strong quantitative agreement is obtained. Our analysis thus provides a robust scheme for identifying the key finite-size (or finite-dimensional) corrections to the mean-field treatment of these paradigmatic glass models.

preprint2022arXiv

Local dynamical heterogeneity in glass formers

We study the local dynamical fluctuations in glass-forming models of particles embedded in $d$-dimensional space, in the mean-field limit of $d\to\infty$. Our analytical calculation reveals that single-particle observables, such as squared particle displacements, display divergent fluctuations around the dynamical (or mode-coupling) transition, due to the emergence of nontrivial correlations between displacements along different directions. This effect notably gives rise to a divergent non-Gaussian parameter, $α_2$. The $d\to\infty$ local dynamics therefore becomes quite rich upon approaching the glass transition. The finite-$d$ remnant of this phenomenon further provides a long sought-after, first-principle explanation for the growth of $α_2$ around the glass transition that is \emph{not based on multi-particle correlations}.

preprint2021arXiv

The dimensional evolution of structure and dynamics in hard sphere liquids

The formulation of the mean-field, infinite-dimensional solution of hard sphere glasses is a significant milestone for theoretical physics. How relevant this description might be for understanding low-dimensional glass-forming liquids, however, remains unclear. These liquids indeed exhibit a complex interplay between structure and dynamics, and the importance of this interplay might only slowly diminish as dimension $d$ increases. A careful numerical assessment of the matter has long been hindered by the exponential increase of computational costs with $d$. By revisiting a once common simulation technique involving the use of periodic boundary conditions modeled on $D_d$ lattices, we here partly sidestep this difficulty, thus allowing the study of hard sphere liquids up to $d=13$. Parallel efforts by Mangeat and Zamponi [Phys. Rev. E 93, 012609 (2016)] have expanded the mean-field description of glasses to finite $d$ by leveraging standard liquid-state theory, and thus help bridge the gap from the other direction. The relatively smooth evolution of both structure and dynamics across the $d$ gap allows us to relate the two approaches, and to identify some of the missing features that a finite-$d$ theory of glasses might hope to include to achieve near quantitative agreement.

preprint2021arXiv

Thermodynamic stability of hard sphere crystals in dimensions 3 through 10

Although much is known about the metastable liquid branch of hard spheres--from low dimension $d$ up to ${d\to\infty}$--its crystal counterpart remains largely unexplored for $d>3$. In particular, it is unclear whether the crystal phase is thermodynamically stable in high dimensions and thus whether a mean-field theory of crystals can ever be exact. In order to determine the stability range of hard sphere crystals, their equation of state is here estimated from numerical simulations, and fluid-crystal coexistence conditions are determined using a generalized Frenkel-Ladd scheme to compute absolute crystal free energies. The results show that the crystal phase is stable at least up to $d=10$, and the dimensional trends suggest that crystal stability likely persists well beyond that point.

preprint2020arXiv

Memory formation in jammed hard spheres

Liquids equilibrated below an onset density share similar inherent states, while above that density their inherent states markedly differ. Although this phenomenon was first reported in simulations over 20 years ago, the physical origin of this memory remains controversial. Its absence from mean-field descriptions, in particular, has long cast doubt on its thermodynamic relevance. Motivated by a recent theoretical proposal, we reassess the onset phenomenology in simulations using a fast hard sphere jamming algorithm and find it both thermodynamically and dimensionally robust. Remarkably, we also uncover a second type of memory associated with a Gardner-like change in behavior along the jamming algorithm.

preprint2019arXiv

Finite-dimensional vestige of spinodal criticality above the dynamical glass transition

Finite-dimensional signatures of spinodal criticality are notoriously difficult to come by. The dynamical transition of glass-forming liquids, first described by mode-coupling theory, is a spinodal instability preempted by thermally activated processes that also limit how close the instability can be approached. We combine numerical tools to directly observe vestiges of the spinodal criticality in finite-dimensional glass formers. We use the swap Monte Carlo algorithm to efficiently thermalise configurations beyond the mode-coupling crossover, and analyze their dynamics using a scheme to screen out activated processes, in spatial dimensions ranging from $d=3$ to $d=9$. We observe a strong softening of the mean-field square-root singularity in $d=3$ that is progressively restored as $d$ increases above $d=8$, in surprisingly good agreement with perturbation theory.

preprint2019arXiv

Postponing the dynamical transition density using competing interactions

Systems of dense spheres interacting through very short-ranged attraction are known from theory, simulations and colloidal experiments to exhibit dynamical reentrance. The liquid state can thus be fluidized to higher densities than otherwise possible with interactions that are purely repulsive or long-ranged attractive. A recent mean-field, infinite-dimensional calculation predicts that the dynamical arrest of the fluid can be further delayed by adding a longer-ranged repulsive contribution to the short-ranged attraction. We examine this proposal by performing extensive numerical simulations in a three-dimensional system. We first find the short-ranged attraction parameters necessary to achieve the densest liquid state, and then explore the parameters space for an additional longer-ranged repulsion that could enhance the effect. In the family of systems studied, no significant (within numerical accuracy) delay of the dynamical arrest is observed beyond what is already achieved by the short-ranged attraction. Possible explanations are discussed.

preprint2019arXiv

Using schematic models to understand the microscopic basis for inverted solubility in $γ$D-crystallin

Inverted solubility--a crystal melting upon cooling--is observed in a handful of proteins, such as carbomonoxy hemoglobin and $γ$D-crystallin. In human $γ$D-crystallin, the phenomenon is associated with the mutation of the 23$^\mathrm{rd}$ residue, a proline, to a threonine, serine or valine. One proposed microscopic mechanism for this effect entails an increase in hydrophobicity upon mutagenesis. Recent crystal structures of a double mutant that includes the P23T mutation allows for a more careful investigation of this proposal. Here, we first measure the surface hydrophobicity of various mutant structures of this protein and determine that it does not discernibly increase upon the mutating the 23$^\mathrm{rd}$ residue. We then investigate the solubility inversion regime with a schematic patchy particle model that includes one of three models for temperature-dependent patch energies: two of the hydrophobic effect, and a more generic description. We conclude that while solubility inversion due to the hydrophobic effect may be possible, microscopic evidence to support it in $γ$D-crystallin is weak. More generally, we find that solubility inversion requires a fine balance between patch strengths and the temperature-dependent contribution, which may explain why inverted solubility is not commonly observed in proteins. In any event, we also find that the temperature-dependent interaction has only a negligible impact on the critical properties of the $γ$D-crystallin, in line with previous experimental observations.

preprint2018arXiv

Clustering and assembly dynamics of a one-dimensional microphase former

Both ordered and disordered microphases ubiquitously form in suspensions of particles that interact through competing short-range attraction and long-range repulsion (SALR). While ordered microphases are more appealing materials targets, understanding the rich structural and dynamical properties of their disordered counterparts is essential to controlling their mesoscale assembly. Here, we study the disordered regime of a one-dimensional (1D) SALR model, whose simplicity enables detailed analysis by transfer matrices and Monte Carlo simulations. We first characterize the signature of the clustering process on macroscopic observables, and then assess the equilibration dynamics of various simulation algorithms. We notably find that cluster moves markedly accelerate the mixing time, but that event chains are of limited help in the clustering regime. These insights will guide further study of three-dimensional microphase formers.

preprint2018arXiv

Correlation lengths in quasi-one-dimensional systems via transfer matrices

Using transfer matrices up to next-nearest-neighbour (NNN) interactions, we examine the structural correlations of quasi-one-dimensional systems of hard disks confined by two parallel lines and hard spheres confined in cylinders. Simulations have shown that the non-monotonic and non-smooth growth of the correlation length in these systems accompanies structural crossovers (Fu et al., Soft Matter, 2017, 13, 3296). Here, we identify the theoretical basis for these behaviour. In particular, we associate kinks in the growth of correlation lengths with eigenvalue crossing and splitting. Understanding the origin of such structural crossovers answers questions raised by earlier studies, and thus bridges the gap between theory and simulations for these reference models.

preprint2018arXiv

Temperature-dependent non-covalent protein-protein interactions explain normal and inverted solubility in a mutant of human gamma D-crystallin

Protein crystal production is a major bottleneck for the structural characterisation of proteins. To advance beyond large-scale screening, rational strategies for protein crystallization are crucial. Understanding how chemical anisotropy (or patchiness) of the protein surface due to the variety of amino acid side chains in contact with solvent, contributes to protein protein contact formation in the crystal lattice is a major obstacle to predicting and optimising crystallization. The relative scarcity of sophisticated theoretical models that include sufficient detail to link collective behaviour, captured in protein phase diagrams, and molecular level details, determined from high-resolution structural information is a further barrier. Here we present two crystals structures for the P23TR36S mutant of gamma D-crystallin, each with opposite solubility behaviour, one melts when heated, the other when cooled. When combined with the protein phase diagram and a tailored patchy particle model we show that a single temperature dependent interaction is sufficient to stabilise the inverted solubility crystal. This contact, at the P23T substitution site, relates to a genetic cataract and reveals at a molecular level, the origin of the lowered and retrograde solubility of the protein. Our results show that the approach employed here may present an alternative strategy for the rationalization of protein crystallization.

preprint2017arXiv

Phase diagram and aggregation dynamics of a monolayer of paramagnetic colloids

We have developed a tunable colloidal system and a corresponding simulation model for studying the phase behavior of particles assembling under the influence of long-range magnetic interactions. A monolayer of paramagnetic particles is subjected to a spatially uniform magnetic field with a static perpendicular component and rapidly rotating in-plane component. The sign and strength of the interactions vary with the tilt angle $θ$ of the rotating magnetic field. For a purely in-plane field, $θ=90^{\circ}$, interactions are attractive and the experimental results agree well with both equilibrium and out-of-equilibrium predictions based on a two-body interaction model. For tilt angles $50^{\circ}\lesssim θ\lesssim 55^{\circ}$, the two-body interaction gives a short-range attractive and long-range repulsive (SALR) interaction, which predicts the formation of equilibrium microphases. In experiments, however, a different type of assembly is observed. Inclusion of three-body (and higher-order) terms in the model does not resolve the discrepancy. We thus further characterize the anomalous behavior by measuring the time-dependent cluster size distribution.

preprint2016arXiv

Assembly of hard spheres in a cylinder: a computational and experimental study

Hard spheres are an important benchmark of our understanding of natural and synthetic systems. In this work, colloidal experiments and Monte Carlo simulations examine the equilibrium and out-of-equilibrium assembly of hard spheres of diameter $σ$ within cylinders of diameter $σ\leq D\leq 2.82σ$. Although in such a system phase transitions formally do not exist, marked structural crossovers are observed. In simulations, we find that the resulting pressure-diameter structural diagram echoes the densest packing sequence obtained at infinite pressure in this range of $D$. We also observe that the out-of-equilibrium self-assembly depends on the compression rate. Slow compression approximates equilibrium results, while fast compression can skip intermediate structures. Crossovers for which no continuous line-slip exists are found to be dynamically unfavorable, which is the source of this difference. Results from colloidal sedimentation experiments at high Péclet number are found to be consistent with the results of fast compressions, as long as appropriate boundary conditions are used. The similitude between compression and sedimentation results suggests that the assembly pathway does not here sensitively depend on the nature of the out-of-equilibrium dynamics.

preprint2016arXiv

Recent Advances in the Theory and Simulation of Model Colloidal Microphase Formers

This mini-review synthesizes our understanding of the equilibrium behavior of particle models with short-range attractive and long-range repulsive (SALR) interactions. These models, which can form stable periodic microphases, aim to reproduce the essence of colloidal suspensions with competing interactions. Ordered structures, however, have yet to be obtained in experiments. In order to better understand the hurdles to periodic microphase assembly, marked theoretical and simulation advances have been made over the last few years. Here, we present recent progress in the study of microphases in models with SALR interactions using liquid-state theory and density-functional theory as well as numerical simulations. Combining these various approaches provides a description of periodic microphases, and give insights into the rich phenomenology of the surrounding disordered regime. Three additional ongoing research directions in the thermodynamics of models with SALR interactions are also presented.