Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userKinetics and thermodynamics of first-order Markov chain copolymerization
274
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
We report a theoretical study of stochastic processes modeling the growth of first-order Markov copolymers, as well as the reversed reaction of depolymerization. These processes are ruled by kinetic equations describing both the attachment and detachment of monomers. Exact solutions are obtained for these kinetic equations in the steady regimes of multicomponent copolymerization and depolymerization. Thermodynamic equilibrium is identified as the state at which the growth velocity is vanishing on average and where detailed balance is satisfied. Away from equilibrium, the analytical expression of the thermodynamic entropy production is deduced in terms of the Shannon disorder per monomer in the copolymer sequence. The Mayo-Lewis equation is recovered in the fully irreversible growth regime. The theory also applies to Bernoullian chains in the case where the attachment and detachment rates only depend on the reacting monomer.
rate research
Read More
This PhD thesis deals with the Markov picture of developed turbulence from the theoretical point of view. The thesis consists of two parts. The first part introduces stochastic thermodynamics, the second part aims at transferring the concepts of stochastic thermodynamics to developed turbulence. / Central in stochastic thermodynamics are Markov processes. An elementary example is Brownian motion. In contrast to macroscopic thermodynamics, the work done and the entropy produced for single trajectories of the Brownian particles are random quantities. Statistical properties of such fluctuating quantities are central in the field of stochastic thermodynamics. Prominent results are so-called fluctuation theorems which express the balance between production and consumption of entropy and generalise the second law. / Turbulent cascades of eddies are assumed to be the predominant mechanism of turbulence generation and fix the statistical properties of developed turbulent flows. An intriguing phenomenon of developed turbulence, known as small-scale intermittency, are violent small-scale fluctuations in flow velocity that exceed any Gaussian prediction. / In analogy to Brownian motion, it is demonstrated in the thesis how the assumption of the Markov property leads to a Markov process for the turbulent cascade that is equivalent to the seminal K62 model. In addition to the K62 model, it is demonstrated how many other models of turbulence can be written as a Markov process, including scaling laws, multiplicative cascades, multifractal models and field-theoretic approaches. Based on the various Markov processes, the production of entropy along the cascade and the corresponding fluctuation theorems is discussed. In particular, experimental data indicates that entropy consumption is linked to small-scale intermittency, and a connection between entropy consumption and an inverse cascade is suggestive.
Estimating the homogeneous ice nucleation rate from undercooled liquid water is at the same time crucial for understanding many important physical phenomena and technological applications, and challenging for both experiments and theory. From a theoretical point of view, difficulties arise due to the long time scales required, as well as the numerous nucleation pathways involved to form ice nuclei with different stacking disorders. We computed the homogeneous ice nucleation rate at a physically relevant undercooling for a single-site water model, taking into account the diffuse nature of ice-water interfaces, stacking disorders in ice nuclei, and the addition rate of particles to the critical nucleus.We disentangled and investigated the relative importance of all the terms, including interfacial free energy, entropic contributions and the kinetic prefactor, that contribute to the overall nucleation rate.There has been a long-standing discrepancy for the predicted homogeneous ice nucleation rates, and our estimate is faster by 9 orders of magnitude compared with previous literature values. Breaking down the problem into segments and considering each term carefully can help us understand where the discrepancy may come from and how to systematically improve the existing computational methods.
We present a principled approach for estimating the matrix of microscopic rates among states of a Markov process, given only its stationary state population distribution and a single average global kinetic observable. We adapt Maximum Caliber, a variational principle in which a path entropy is maximized over the distribution of all the possible trajectories, subject to basic kinetic constraints and some average dynamical observables. We show that this approach leads, under appropriate conditions, to the continuous-time master equation and a Smoluchowski-like equation that is valid for both equilibrium and non-equilibrium stationary states. We illustrate the method by computing the solvation dynamics of water molecules from molecular dynamics trajectories.
We verify the finite time fluctuation theorem for a linear Ising chain at its ends in contact with heat reservoirs. Analytic results are derived for a chain consisting of only two spins. The system can be mapped onto a model for particle transport, namely the symmetric exclusion process, in contact with thermal and particle reservoirs. We modify the symmetric exclusion process to represent a thermal engine and reproduce universal features of the efficiency at maximum power.
The standard formulation of thermostatistics, being based on the Boltzmann-Gibbs distribution and logarithmic Shannon entropy, describes idealized uncorrelated systems with extensive energies and short-range interactions. In this letter, we use the fundamental principles of ergodicity (via Liouvilles theorem), the self-similarity of correlations, and the existence of the thermodynamic limit to derive generalized forms of the equilibrium distribution for long-range-interacting systems. Significantly, our formalism provides a justification for the well-studied nonextensive thermostatistics characterized by the Tsallis distribution, which it includes as a special case. We also give the complementary maximum entropy derivation of the same distributions by constrained maximization of the Boltzmann-Gibbs-Shannon entropy. The consistency between the ergodic and maximum entropy approaches clarifies the use of the latter in the study of correlations and nonextensive thermodynamics.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
