Communication: Computing the Helmholtz capacitance of charged insulatorelectrolyte interfaces from the supercell polarization
Abstract
Supercell modeling of an electrical double layer (EDL) at electrified solidelectrolyte interfaces is a challenge. The net polarization of EDLs arising from the fixed chemical composition setup leads to uncompensated EDLs under periodic boundary condition and convolutes the calculation of the Helmholtz capacitance [C. Zhang and M. Sprik, Phys. Rev. B 94, 245309 (2016)]. Here we provide a new formula based on the supercell polarization at zero electric field Ē = 0 (i.e., standard Ewald boundary condition) to calculate the Helmholtz capacitance of charged insulatorelectrolyte interfaces and validate it using atomistic simulations. Results are shown to be independent of the supercell size. This formula gives a shortcut to compute the Helmholtz capacitance without locating the zero net charge state of EDL and applies directly to any standard molecular dynamics code where the electrostatic interactions are treated by the Ewald summation or its variants.
 Publication:

Journal of Chemical Physics
 Pub Date:
 July 2018
 DOI:
 10.1063/1.5038639
 arXiv:
 arXiv:1805.00246
 Bibcode:
 2018JChPh.149c1103Z
 Keywords:

 Condensed Matter  Soft Condensed Matter
 EPrint:
 J. Chem. Phys. 149, 031103 (2018)