When two electrolyte-immersed electrodes have different temperatures, a voltage $\Delta \psi$ can be measured between them. This electrolyte Seebeck effect is usually explained by cations and anions flowing differently in thermal gradients. However, our molecular dynamics simulations of aqueous electrolytes reveal a large temperature-dependent potential drop $\chi$ near blocking electrodes caused by water layering and orientation. The difference in surface potentials at hot and cold electrodes is more important to the Seebeck effect than ionic thermodiffusion, $\Delta \psi \sim \chi_{ \rm hot}-\chi_{ \rm cold}$.
Categories: physics.chem-ph cond-mat.soft physics.comp-ph