Issue 41, 2023

Molecular dynamics investigation of benzoic acid in confined spaces

Abstract

Classical molecular dynamics simulations are carried out to investigate the aggregation of supercooled benzoic acid in confined spaces. Nanocavities, nanotubes and nanolayers are defined by restricting the periodicity of the simulation to zero, one or two dimensions, with boundaries set by adjustable, general, and computationally cheap van der Waals barriers. The effect of different confinement geometries is explored. It is found that the confinement impacts the liquid collective dynamics, strengthening the correlations that affect the motion of distant molecules. Overall, confinement determines up to a tenfold increase of the viscosity of the liquid and strongly slows down the rotational correlation times. Aggregation mediated by interactions with the walls and partial polarization of the liquid are observed. Additionally, transitions to high-density liquid states occur when stiffer barriers are used. In general, a reduced accessible amount of phase space fosters the struggle for a closer packing to relieve unfavorable atom–atom contacts, while maximizing the attractive ones. In benzoic acid, this implies that the hydrogen bond network is organized more efficiently in high density states.

Graphical abstract: Molecular dynamics investigation of benzoic acid in confined spaces

Supplementary files

Article information

Article type
Paper
Submitted
21 Jun 2023
Accepted
23 Sep 2023
First published
26 Sep 2023
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2023,25, 28006-28019

Molecular dynamics investigation of benzoic acid in confined spaces

L. Sironi, G. Macetti and L. Lo Presti, Phys. Chem. Chem. Phys., 2023, 25, 28006 DOI: 10.1039/D3CP02886K

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