Molecular dynamics investigation of the influence of the hydrogen bond networks in ethanol/water mixtures on dielectric spectra

Cardona, Javier and Sweatman, Martin B. and Lue, Leo (2018) Molecular dynamics investigation of the influence of the hydrogen bond networks in ethanol/water mixtures on dielectric spectra. Journal of Physical Chemistry B, 122 (4). pp. 1505-1515. ISSN 1520-6106 (https://doi.org/10.1021/acs.jpcb.7b12220)

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Abstract

The dielectric response of fluids to electromagnetic radiation in the microwave region originates from processes occurring at the molecular level. Understanding these processes in more detail is relevant to many fields, such as microwave heating, fluid mixing, and separation technologies. In this work, we use molecular dynamics simulations to study the dielectric spectra of ethanol/water mixtures. We compare our predictions with experimental results at different compositions. We show how the dielectric response can be estimated to a high level of accuracy using three dielectric relaxations: a dominant and slower process at microwave frequencies and two faster processes. A deeper study of the dynamics of the hydrogen bond network formed in these systems reveals how collective processes between the individual species are the origin of the final dielectric response. Our results agree with the "wait-and-switch" mechanism, which describes the dynamics of the hydrogen bond network as the combination of two processes: the fast breakage and formation of individual hydrogen bonds and the subsequent reorganization of the entire network once this process becomes energetically favorable. Since the dielectric response is related to dipole reorientations in the system, it is directly linked to these mechanisms.

ORCID iDs

Cardona, Javier ORCID logoORCID: https://orcid.org/0000-0002-9284-1899, Sweatman, Martin B. and Lue, Leo ORCID logoORCID: https://orcid.org/0000-0002-4826-5337;
CORE (COnnecting REpositories)