Predicting the behaviour of near-critical and supercritical alcohols at microwave frequencies: Validation of molecular dynamic simulations as a tool that can substitute for measurements under extreme experimental conditions

Robinson, D. ORCID: 0000-0003-2760-7163, Irvine, D.J., Robinson, J.P., Lester, E.H., Kingman, S.W. and Dimitrakis, G., 2019. Predicting the behaviour of near-critical and supercritical alcohols at microwave frequencies: Validation of molecular dynamic simulations as a tool that can substitute for measurements under extreme experimental conditions. The Journal of Supercritical Fluids, 146, pp. 165-171. ISSN 0896-8446

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Abstract

Equilibrium and non-equilibrium molecular dynamic simulations, predicting the dielectric properties of near-critical and supercritical methanol and ethanol at microwave frequencies have been carried out. The autocorrelation functions of the dielectric relaxation, show dependency on the slow component at the near-critical region for both alcohols. At the supercritical region, two competing relaxation mechanisms are observed, related to the large breakdown of the hydrogen-bonding network and the degree of clustering between the molecules. This approach closely matches experimental data at microwave frequencies and identical temperature and pressure conditions, validating the predictions of how the molecular structure and dynamics manifest themselves into the complex permittivity and dielectric relaxation behaviour. Thus, introducing a modelling-based solution to deliver accurate dielectric property values for materials at supercritical conditions for “a priori” screening of solvents, whilst removing the need to overcome engineering and safety challenges associated with the development of experimental equipment to practically generate such data.

Item Type: Journal article
Publication Title: The Journal of Supercritical Fluids
Creators: Robinson, D., Irvine, D.J., Robinson, J.P., Lester, E.H., Kingman, S.W. and Dimitrakis, G.
Publisher: Elsevier
Date: 2019
Volume: 146
ISSN: 0896-8446
Identifiers:
NumberType
10.1016/j.supflu.2019.01.018DOI
S0896844618304662Publisher Item Identifier
Divisions: Schools > School of Science and Technology
Depositing User: Jonathan Gallacher
Date Added: 22 Feb 2019 16:10
Last Modified: 22 Feb 2019 16:10
URI: http://irep.ntu.ac.uk/id/eprint/35797

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