TY - JOUR
T1 - Simulation of charged systems in heterogeneous dielectric media via a true energy functional
AU - Jadhao, Vikram
AU - Solis, Francisco
AU - De La Cruz, Monica Olvera
PY - 2012/11/27
Y1 - 2012/11/27
N2 - For charged systems in heterogeneous dielectric media, a key obstacle for molecular dynamics (MD) simulations is the need to solve the Poisson equation in the media. This obstacle can be bypassed using MD methods that treat the local polarization charge density as a dynamic variable, but such approaches require access to a true free energy functional, one that evaluates to the equilibrium electrostatic energy at its minimum. In this Letter, we derive the needed functional. As an application, we develop a Car-Parrinello MD method for the simulation of free charges present near a spherical emulsion droplet separating two immiscible liquids with different dielectric constants. Our results show the presence of nonmonotonic ionic profiles in the dielectric with a lower dielectric constant.
AB - For charged systems in heterogeneous dielectric media, a key obstacle for molecular dynamics (MD) simulations is the need to solve the Poisson equation in the media. This obstacle can be bypassed using MD methods that treat the local polarization charge density as a dynamic variable, but such approaches require access to a true free energy functional, one that evaluates to the equilibrium electrostatic energy at its minimum. In this Letter, we derive the needed functional. As an application, we develop a Car-Parrinello MD method for the simulation of free charges present near a spherical emulsion droplet separating two immiscible liquids with different dielectric constants. Our results show the presence of nonmonotonic ionic profiles in the dielectric with a lower dielectric constant.
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U2 - 10.1103/PhysRevLett.109.223905
DO - 10.1103/PhysRevLett.109.223905
M3 - Article
AN - SCOPUS:84870209083
SN - 0031-9007
VL - 109
JO - Physical Review Letters
JF - Physical Review Letters
IS - 22
M1 - 223905
ER -