arXiv subjects

Michael R. Buche

Publications and source records attributed to Michael R. Buche.

8 recordsLinked to original sources

arXiv2026

Extensible links in a broad class of single polymer chain models

The physics of polymer chains is often probed using molecular stretching experiments and various idealized single-chain models. The majority of these models consist of a discrete sequence of links, which may be treated as rigid or extensible. Although such models are well established and many specific extensible variants have been proposed, no generally applicable theory has been presented. Moreover, most existing treatments are heuristic rather than systematically and rigorously derived. This critical gap is closed here through the development of a generally applicable asymptotic theory for including link extensibility in a broad class of discrete models for single-chain thermodynamics. The theory is verified analytically using the freely jointed chain and validated numerically using the freely rotating chain. The resulting approximation is first-order accurate in inverse link stiffness, with quadratically decreasing error, and recovers extensible behavior across all link stiffnesses from a single rigid-link reference calculation.

cond-mat.stat-mech↗

arXiv2026

Link length and energy fluctuations in extensible freely jointed chains

The freely jointed chain is often applied to model the thermodynamics of single polymer chains, but the traditional formulation of the model lacks internal energy changes due to bond stretching. For this reason, the extensible freely jointed chain model includes a potential energy function, typically harmonic, that governs the length of each link in the chain. Among the other quantities of interest that are subject to thermal fluctuations, these link lengths and energies too fluctuate about their ensemble average values. Since a plethora of models for polymer chains and networks incorporate chain dissociation as a function of either link length or energy, these fluctuations are crucial to understand and quantify. Motivated by this fact, fluctuations in link length and energy are analyzed within a freely jointed chain under an applied force. These fluctuations are quantified through their average values, standard deviations, and probability distributions. Across all values, asymptotically correct analytic relations and their less ergonomic exact counterparts are introduced. The asymptotic relations are verified to be accurate through direct comparison and to be correct within transcendentally small terms through error analysis. In certain cases, the fluctuations are shown to be approximately normally distributed. Hereafter, model components predicated on link length or energy ought to account for these fluctuations.

cond-mat.stat-mech↗

arXiv2026

Thermodynamic fluctuations in freely jointed chains under force

It is common to study polymer physics through the use of idealized single-chain models, and the most popular of these is the freely jointed chain model. In certain thermodynamic ensembles, statistical mechanical treatment of this model is analytically tractable or sometimes exactly solvable. This enables useful relations to be ascertained, like the expected chain end-to-end length as a function of an applied force. However, most of these relations return ensemble averages, which are values with inherent uncertainty, as opposed to deterministic values with no variance. This is an important distinction to understand and quantify, because the majority of studies to date involving single-chain models effectively treat these values as deterministic rather than fluctuating. To address this issue, thermodynamic fluctuations are examined in the freely jointed chain model. Specifically, the probability densities and standard deviations of the longitudinal, lateral, transverse, and radial portions of the chain extension, as well as the extension and link angles, are examined for different numbers of links and applied forces. Fluctuations in these quantities are shown to be considerable until the applied force becomes large. Increasing the number of links in the chain gradually reduces fluctuations in all quantities except for the link angles, since they are independent for freely jointed chains in the isotensional ensemble. Quantities are obtained analytically whenever possible and numerically otherwise. Overall, these results provide intuitive admonitions to consider when modeling the stretching of single polymer chains or the deformation of entire polymer networks.

cond-mat.stat-mech↗

arXiv2024

Statistical mechanical model for crack growth

Analytic relations that describe crack growth are vital for modeling experiments and building a theoretical understanding of fracture. Upon constructing an idealized model system for the crack and applying the principles of statistical thermodynamics, it is possible to formulate the rate of thermally activated crack growth as a function of load, but the result is analytically intractable. Here, an asymptotically correct theory is used to obtain analytic approximations of the crack growth rate from the fundamental theoretical formulation. These crack growth rate relations are compared to those that exist in the literature and are validated with respect to Monte Carlo calculations and experiments. The success of this approach is encouraging for future modeling endeavors that might consider more complicated fracture mechanisms, such as inhomogeneity or a reactive environment.

cond-mat.stat-mech↗

arXiv2024

Modeling single-molecule stretching experiments using statistical thermodynamics

Single-molecule stretching experiments are widely utilized within the fields of physics and chemistry to characterize the mechanics of individual bonds or molecules, as well as chemical reactions. Analytic relations describing these experiments are valuable, and these relations can be obtained through the statistical thermodynamics of idealized model systems representing the experiments. Since the specific thermodynamic ensembles manifested by the experiments affect the outcome, primarily for small molecules, the stretching device must be included in the idealized model system. Though the model for the stretched molecule might be exactly solvable, including the device in the model often prevents analytic solutions. In the limit of large or small device stiffness, the isometric or isotensional ensembles can provide effective approximations, but the device effects are missing. Here, a dual set of asymptotically correct statistical thermodynamic theories are applied to develop accurate approximations for the full model system that includes both the molecule and the device. The asymptotic theories are first demonstrated to be accurate using the freely jointed chain model, and then using molecular dynamics calculations of a single polyethylene chain.

cond-mat.stat-mech↗

arXiv2023

Freely jointed chain models with extensible links

Analytical relations for the mechanical response of single polymer chains are valuable for modeling purposes, on both the molecular and the continuum scale. These relations can be obtained using statistical thermodynamics and an idealized single-chain model, such as the freely jointed chain model. To include bond stretching, the rigid links in the freely jointed chain model can be made extensible, but this almost always renders the model analytically intractable. Here, an asymptotically correct statistical thermodynamic theory is used to develop analytic approximations for the single-chain mechanical response of this model. The accuracy of these approximations is demonstrated using several link potential energy functions. This approach can be applied to other single-chain models, and to molecular stretching in general.

cond-mat.stat-mech↗

arXiv2021

Chain breaking in the statistical mechanical constitutive theory of polymer networks

Elastomers are used in a wide range of applications because of their large strain to failure, low density, and tailorable stiffness and toughness. The mechanical behavior of elastomers derives mainly from the entropic elasticity of the underlying network of polymer chains. Elastomers under large deformation experience bonds breaking within the polymer network. This breaking of chains damages the network, can lead to material failure, and can be utilized as an energy dissipation mechanism. In the case of reversible bonds, broken chains may reform and heal the damage in the network. If the reversible bonds are dynamic, chains constantly break and reform and create a transient network. A fundamental constitutive theory is developed to model the mechanics of these polymer networks. A statistical mechanical derivation is conducted to yield a framework that takes in an arbitrary single-chain model (a Hamiltonian) and outputs: the single-chain mechanical response, the breaking and reforming kinetics, the equilibrium distribution of chains in the network, and the partial differential equations governing the deformation-coupled network evolution. This statistical mechanical framework is then brought into the continuum scale by using macroscopic thermodynamic constitutive theory to obtain a constitutive relation for the Cauchy stress. The potential-supplemented freely jointed chain ($u$FJC) model is introduced, and a parametric study of its mechanical response and breaking kinetics is provided. This single-chain model is then implemented within the constitutive framework, which we specialize and apply in two exemplary cases: the mechanical response and irreversible breakdown of a multinetwork elastomer, and the mechanical response of a dual crosslink gel. After providing a parametric study of the general constitutive model, we apply it to a hydrogel with reversible metal-coordination crosslinks.

cond-mat.soft↗

arXiv2020

Statistical mechanical constitutive theory of polymer networks: The inextricable links between distribution, behavior, and ensemble

A fundamental theory is presented for the mechanical response of polymer networks undergoing large deformation which seamlessly integrates statistical mechanical principles with macroscopic thermodynamic constitutive theory. Our formulation permits the consideration of arbitrary polymer chain behaviors when interactions among chains may be neglected. This careful treatment highlights the naturally occurring correspondence between single-chain mechanical behavior and the equilibrium distribution of chains in the network, as well as the correspondences between different single-chain thermodynamic ensembles. We demonstrate these important distinctions with the extensible freely jointed chain model. This statistical mechanical theory is then extended to the continuum scale, where we utilize traditional macroscopic constitutive theory to ultimately retrieve the Cauchy stress in terms of the deformation and polymer network statistics. Once again using the extensible freely jointed chain model, we illustrate the importance of the naturally occurring statistical correspondences through their effects on the stress-stretch response of the network. We additionally show that these differences vanish when the number of links in the chain becomes sufficiently large enough, and discuss why certain methods perform better than others before this limit is reached.

cond-mat.soft↗