NOTICE: Due to a lapse in annual appropriations, most of this website is not being updated. Learn more.
Form submissions will still be accepted but will not receive responses at this time. Sections of this site for programs using non-appropriated funds (such as NVLAP) or those that are excepted from the shutdown (such as CHIPS and NVD) will continue to be updated.
An official website of the United States government
Here’s how you know
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
Secure .gov websites use HTTPS
A lock (
) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.
Solvent effects determine the sign of the charges of maximum entropy and capacitance at silver electrodes
Published
Author(s)
Ravishankar Sundararaman, Kathleen Schwarz
Abstract
Fully harnessing electrochemical interfaces for reactions requires a detailed understanding of solvent effects in the electrochemical double layer. Predicting the significant impact of solvent on entropic and electronic properties of electrochemical interfaces has remained an open challenge of computational electrochemistry. Using molecular dynamics simulations of silver-water and silver-acetonitrile interfaces, we show that switching the solvent changes the signs for both the charges of maximum capacitance (CMC) and maximum entropy (CME). Contrasting the capacitance and CME behavior of these two interfaces, we demonstrate that the preferred orientation of the solvent molecule and the corresponding charge density determine the sign of the CMC and CME, and hence, the qualitatively-different charge asymmetry of the electrochemical interface.
Sundararaman, R.
and Schwarz, K.
(2023),
Solvent effects determine the sign of the charges of maximum entropy and capacitance at silver electrodes, Journal of Chemical Physics, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=936201
(Accessed October 8, 2025)