TY - JOUR
T1 - Free-energy functionals of the electrostatic potential for Poisson-Boltzmann theory
AU - Jadhao, Vikram
AU - Solis, Francisco
AU - De La Cruz, Monica Olvera
PY - 2013/8/12
Y1 - 2013/8/12
N2 - In simulating charged systems, it is often useful to treat some ionic components of the system at the mean-field level and solve the Poisson-Boltzmann (PB) equation to get their respective density profiles. The numerically intensive task of solving the PB equation at each step of the simulation can be bypassed using variational methods that treat the electrostatic potential as a dynamic variable. But such approaches require the access to a true free-energy functional: a functional that not only provides the correct solution of the PB equation upon extremization, but also evaluates to the true free energy of the system at its minimum. Moreover, the numerical efficiency of such procedures is further enhanced if the free-energy functional is local and is expressed in terms of the electrostatic potential. Existing PB functionals of the electrostatic potential, while possessing the local structure, are not free-energy functionals. We present a variational formulation with a local free-energy functional of the potential. In addition, we also construct a nonlocal free-energy functional of the electrostatic potential. These functionals are suited for employment in simulation schemes based on the ideas of dynamical optimization.
AB - In simulating charged systems, it is often useful to treat some ionic components of the system at the mean-field level and solve the Poisson-Boltzmann (PB) equation to get their respective density profiles. The numerically intensive task of solving the PB equation at each step of the simulation can be bypassed using variational methods that treat the electrostatic potential as a dynamic variable. But such approaches require the access to a true free-energy functional: a functional that not only provides the correct solution of the PB equation upon extremization, but also evaluates to the true free energy of the system at its minimum. Moreover, the numerical efficiency of such procedures is further enhanced if the free-energy functional is local and is expressed in terms of the electrostatic potential. Existing PB functionals of the electrostatic potential, while possessing the local structure, are not free-energy functionals. We present a variational formulation with a local free-energy functional of the potential. In addition, we also construct a nonlocal free-energy functional of the electrostatic potential. These functionals are suited for employment in simulation schemes based on the ideas of dynamical optimization.
UR - http://www.scopus.com/inward/record.url?scp=84883865866&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84883865866&partnerID=8YFLogxK
U2 - 10.1103/PhysRevE.88.022305
DO - 10.1103/PhysRevE.88.022305
M3 - Article
C2 - 24032831
AN - SCOPUS:84883865866
SN - 1539-3755
VL - 88
JO - Physical Review E - Statistical, Nonlinear, and Soft Matter Physics
JF - Physical Review E - Statistical, Nonlinear, and Soft Matter Physics
IS - 2
M1 - 022305
ER -