Modified Poisson-Boltzmann theory for polyelectrolytes in monovalent salt solutions with finite-size ions

: Vahid, Hossein; Scacchi, Alberto; Yang, Xiang; Ala-Nissila, Tapio; Sammalkorpi, Maria

Publisher: AIP Publishing

: MELVILLE

: 2022

: Journal of Chemical Physics

: JOURNAL OF CHEMICAL PHYSICS

: J CHEM PHYS

: 214906

: 156

: 21

: 11

: 0021-9606

: 1089-7690

DOI: https://doi.org/10.1063/5.0092273

We present a soft-potential-enhanced Poisson-Boltzmann (SPB) theory to efficiently capture ion distributions and electrostatic potential around rodlike charged macromolecules. The SPB model is calibrated with a coarse-grained particle-based model for polyelectrolytes (PEs) in monovalent salt solutions as well as compared to a full atomistic molecular dynamics simulation with the explicit solvent. We demonstrate that our modification enables the SPB theory to accurately predict monovalent ion distributions around a rodlike PE in a wide range of ion and charge distribution conditions in the weak-coupling regime. These include excess salt concentrations up to 1M and ion sizes ranging from small ions, such as Na+ or Cl-, to softer and larger ions with a size comparable to the PE diameter. The work provides a simple way to implement an enhancement that effectively captures the influence of ion size and species into the PB theory in the context of PEs in aqueous salt solutions. Published under an exclusive license by AIP Publishing.