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Stefano A Mezzasalma

Publications and source records attributed to Stefano A Mezzasalma.

5 recordsLinked to original sources

The special theory of Brownian relativity: equivalence principle for dynamic and static random paths and uncertainty relation for diffusion.

The theoretical basis of a recent theory of Brownian relativity for polymer solutions is deepened and reexamined. After the problem of relative diffusion in polymer solutions is addressed, its two postulates are formulated in all generality. The former builds a statistical equivalence between (uncorrelated) timelike and shapelike reference frames, that is, among dynamical trajectories of liquid molecules and static configurations of polymer chains. The latter defines the "diffusive horizon" as the invariant quantity to work with in the special version of the theory. Particularly, the concept of universality in polymer physics corresponds in Brownian relativity to that of covariance in the Einstein formulation. Here, a "universal" law consists of a privileged observation, performed from the laboratory rest frame and agreeing with any diffusive reference system. From the joint lack of covariance and simultaneity implied by the Brownian Lorentz-Poincaré transforms, a relative uncertainty arises, in a certain analogy with quantum mechanics. It is driven by the difference between local diffusion coefficients in the liquid solution. The same transformation class can be used to infer Fick's second law of diffusion, playing here the role of a gauge invariance preserving covariance of the spacetime increments. An overall, noteworthy conclusion emerging from this view concerns the statistics of (i) static macromolecular configurations and (ii) the motion of liquid molecules, which would be much more related than expected.

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Configurational statistics of macromolecules in solution from correlations of liquid molecules.

We address the relevant quest for a simple formalism describing the microstructure of liquid solutions of polymer chains. On the basis of a recent relativistic-type picture of self-diffusion in (simple) liquids named Brownian relativity (BWR), a covariant van Hove's distribution function in a Vineyard-like convolution approximation is proposed to relate the statistical features of liquid and chain molecules forming a dilute polymer solution. It provides an extension of the Gaussian statistics of ideal chains to correlated systems, allowing an analysis of macromolecular configurations in solution by the only statistical properties of the liquid units (and vice versa). However, the mathematical solution to this issue is not straightforward because, when the liquid and polymer van Hove's functions are equated, an inverse problem takes place. It presents some conceptual analogies with a scattering experiment in which the correlation of the liquid molecules acts as the radiation source and the macromolecule as the scatterer. After inverting the equation by a theorem coming from the Tikhonov's approach, it turns out that the probability distribution function of a real polymer can be expressed from a static Ornstein-Uhlenbeck process, modified by correlations. This result is used to show that the probability distribution of a true self-avoiding walk polymer (TSWP) can be modeled as a universal Percus-Yevick hard-sphere solution for the total correlation function of the liquid units. This method suits in particular the configurational analysis of single macromolecules. The analytical study of arbitrary many-polymer systems may require further mathematical investigation.

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Real polymer size from the ideal chain molecules model in a diffusive Minkowskian spacetime.

The universal exponent (nu(r)) of the real polymer size (i.e., the excluded volume chain) is derived from constraining the ideal coil model (nu(i) = 12) to a Minkowski-type diffusive spacetime. The square end-to-end distance was expanded in wavenumber power series, whence the leading contribution is extracted according to previously proposed Lorentz transforms acting in Brownian media. In the end, it turns out nu(i) approximately equal to nu(r) sin 1, in good agreement with predictions of the phase transition theory for critical phenomena.

Kinetics↗

A general criterion based on the implicit function theorem to model aggregation and adsorption in colloidal dispersions.

This paper, which may interest not only colloid scientists and physical chemists but also applied mathematicians, completes some previous results on aqueous silicon nitride dispersions. Experimental data on adsorption from liquid solution were first obtained by a titration method and then used to derive the number of solid particles from an equilibrium constraint. To discuss the complex mechanisms affecting simultaneous solid particle aggregation and small ion adsorption at the solid/liquid interface, the Dini implicit function theorem (DT) has been applied to the equilibrium condition for a former suspension Gibbs free energy. It was able to relate the average particle number to the ion concentration adsorbed, but not to unequivocally specify their dependence on the liquid phase pH. We attempt here to model aggregation both through bulk and interfacial quantities. The generalized DT-based criterion has first been formulated in all generality, and then adopted according to a wider investigation. The results obtained confirm the original guess, i.e., to regard solid aggregation as dominated by interfacial mechanisms.

Adsorption↗

Scaling laws for geometry and macromolecules in solution: an interdisciplinary approach to statistical and thermal physics.

An interdisciplinary program, dealing with statistics within basic geometry, is presented and discussed across some modern physics. Its fundamentals are of general interest in physical chemistry, but specially suit investigating conformational statistics and universal scaling of polymer chains in solution. We pointed out an equivalence principle for shape and statistics that can straightforwardly link probability distributions to geometrical quantities at smaller length scales. The average polymer size is thus expected following analytically from the energy surface of its dimeric unit. This would finally suggest extending molecular mechanics to a geometrical setting that reaches the limit of vanishing scales.

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