Modeling Charge-Sign Asymmetric Solvation Free Energies With Nonlinear Boundary Conditions

Jaydeep P. Bardhan; Matthew G. Knepley

doi:10.1063/1.4897324

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arXiv · 1409.7418

Modeling Charge-Sign Asymmetric Solvation Free Energies With Nonlinear Boundary Conditions

Jaydeep P. Bardhan·Matthew G. Knepley

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Abstract

We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory but replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley "bracelet" and "rod" test problems [J. Phys. Chem. B, v. 112:2408, 2008]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry.

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Jaydeep P. Bardhan, Matthew G. Knepley. 2014-09-25. Modeling Charge-Sign Asymmetric Solvation Free Energies With Nonlinear Boundary Conditions. https://doi.org/10.1063/1.4897324

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