Dielectric permittivity of water confined in stacks of charged lipid layers: extracting profiles from molecular dynamics simulations using a modified Poisson-Boltzmann equation

Abstract: Most organic and inorganic surfaces (e.g., glass, nucleic acids or lipid membranes) become charged in aqueous solutions. The resulting ionic distribution induces effective interactions between the charged surfaces. Stacks of like-charged lipid bilayers immersed in multivalent ion solutions exhibit strong coupling (SC) effects, where ion correlations cause counter-intuitive membrane attraction. A similar attraction observed with monovalent ions is explained by SC theory through reduced dielectric permittivity under confinement. To explore this phenomenon, we propose a modified Poisson-Boltzmann (mPB) model with spatially varying dielectric permittivity and explicit Born solvation energy for ions. We use the model to investigate the dielectric permittivity profile of confined water in molecular dynamics simulations of charged lipid layers stacks at varying hydration levels, and compare the results with alternative computational methods. The model captures a sharp decrease in permittivity as the system enters the attractive regime, converging to a plateau value that we attribute to lipid headgroups. The generic nature of the mPB framework allows application to other systems, such as other biological interfaces or solid walls, provided ions follow Boltzmann statistics.