Osmotic Method for Calculating Surface Pressure of Monolayers in Molecular Dynamics Simulations

J Chem Theory Comput. 2022 Apr 12;18(4):2042-2046. doi: 10.1021/acs.jctc.2c00109. Epub 2022 Mar 7.

Abstract

Surface pressure is a fundamental thermodynamic property related to the activity of molecules at interfaces. In molecular simulations, it is typically calculated from its definition: the difference between the surface tension of the air-water and air-surfactant interfaces. In this Letter, we show how to connect the surface pressure with a two-dimensional osmotic pressure and how to take advantage of this analogy to obtain a practical method of calculating surface pressure-area isotherms in molecular simulation. As a proof-of-concept, compression curves of zwitterionic and ionic surfactant monolayers were obtained using the osmotic approach and the curves were compared with the ones from the traditional pressure tensor-based scheme. The results shown an excellent agreement between both alternatives. Advantageously, the osmotic approach is simple to use and allows to obtain the surface pressure-area isotherm on the fly with a single simulation using equilibration stages.

MeSH terms

  • Molecular Dynamics Simulation*
  • Osmosis
  • Pulmonary Surfactants*
  • Surface Properties
  • Surface Tension
  • Surface-Active Agents
  • Water

Substances

  • Pulmonary Surfactants
  • Surface-Active Agents
  • Water