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Free Volume in Thermodynamics

A special issue of Entropy (ISSN 1099-4300). This special issue belongs to the section "Thermodynamics".

Deadline for manuscript submissions: closed (30 November 2022) | Viewed by 3040

Special Issue Editor


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Guest Editor
1. Department of Physics, The University of Akron, Akron, OH 44325, USA
2. Department of Polymer Science, The University of Akron, Akron, OH 44325, USA
Interests: phase transitions and critical phenomena; non-equilibrium statistical thermodynamics; bulk and confined space thermodynamics; polymer physics; solution theory; combinatorics and graph theory; renormalization group and field theory
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The concept of free volume and its distribution are used to explain molecular motion and compressibility in systems such as liquids and solids (amorphous or crystalline). Usually, free volume increases with increasing temperature, and so it is central to the concept of molecular motion, diffusion, mobility, cavity structures and emergent elasticity. For this reason, it plays an important role in thermodynamics such as in glass transitions, as evidenced by the spectacular success of the phenomenological Doolittle model. The experimental determination of free volume (e.g., through positron annihilation spectroscopy) and its explanation in terms of theoretical approaches (e.g., hole theory) or computer simulations (e.g., using Voronoi tessellation) depends on how free volume is defined. This Special Issue is an attempt to draw together various authors who can contribute to different aspects of this important field in thermodynamics, its historic development, and its relationship with other modern theories, such as the mode-coupling theory.

Prof. Dr. Purushottam D. Gujrati
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Entropy is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • free volume
  • void
  • hole
  • microvoid
  • distribution
  • polymers
  • glass transition
  • diffusion
  • self-diffusion
  • thermal fluctuations
  • activation processes

Published Papers (1 paper)

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Review

44 pages, 11887 KiB  
Review
Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers
by Vladimir N. Novikov and Alexei P. Sokolov
Entropy 2022, 24(8), 1101; https://doi.org/10.3390/e24081101 - 10 Aug 2022
Cited by 6 | Viewed by 2561
Abstract
Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature Tg, whether there is an underlying [...] Read more.
Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature Tg, whether there is an underlying thermodynamic transition at some finite temperature below Tg, what the role of cooperativity and heterogeneity are, and many other questions continue to be topics of active discussions. This review focuses on the mechanisms that control the steepness of the temperature dependence of structural relaxation (fragility) in glass-forming liquids. We present a brief overview of the basic theoretical models and their experimental tests, analyzing their predictions for fragility and emphasizing the successes and failures of the models. Special attention is focused on the connection of fast dynamics on picosecond time scales to the behavior of structural relaxation on much longer time scales. A separate section discusses the specific case of polymeric glass-forming liquids, which usually have extremely high fragility. We emphasize the apparent difference between the glass transitions in polymers and small molecules. We also discuss the possible role of quantum effects in the glass transition of light molecules and highlight the recent discovery of the unusually low fragility of water. At the end, we formulate the major challenges and questions remaining in this field. Full article
(This article belongs to the Special Issue Free Volume in Thermodynamics)
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