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Updated: Dec 18, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing
Sebastian Pawlus1, Andrzej Grzybowski2, Sławomir Kołodziej3
1August Chełkowski Institute of Physics, University of Silesia in Katowice, ul. 75 Pułku Piechoty 1, 41-500, Chorzów, Poland. sebastian.pawlus@us.edu.pl.
Abstract:
In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to detect thermodynamic regions characterized by intermolecular interactions of different type and complexity for a given material in the wide pressure-volume-temperature domain even if its typical form with constant scaling exponent is not obeyed. Moreover, we quantify the observed decoupling between dielectric and mechanical relaxations of the material in the density scaling regime. The suggested methods of analyses and their interpretations open new prospects for formulating models based on proper effective intermolecular potentials describing physicochemical phenomena near the glass transition.
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