Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Charge fluctuations from molecular simulations in the constant-potential ensemble
 
research article

Charge fluctuations from molecular simulations in the constant-potential ensemble

Scalfi, Laura
•
Limmer, David T.
•
Coretti, Alessandro  
Show more
May 21, 2020
Physical Chemistry Chemical Physics

We revisit the statistical mechanics of charge fluctuations in capacitors. In constant-potential classical molecular simulations, the atomic charges of electrode atoms are treated as additional degrees of freedom which evolve in time so as to satisfy the constraint of fixed electrostatic potential for each configuration of the electrolyte. The present work clarifies the role of the overall electroneutrality constraint, as well as the link between the averages computed within the Born-Oppenheimer approximation and that of the full constant-potential ensemble. This allows us in particular to derive a complete fluctuation-dissipation relation for the differential capacitance, that includes a contribution from the charge fluctuations (around the charges satisfying the constant-potential and electroneutrality constraints) also present in the absence of an electrolyte. We provide a simple expression for this contribution from the elements of the inverse of the matrix defining the quadratic form of the fluctuating charges in the energy. We then illustrate numerically the validity of our results, and recover the expected continuum result for an empty capacitor with structureless electrodes at large inter-electrode distances. By considering a variety of liquids between graphite electrodes, we confirm that this contribution to the total differential capacitance is small compared to that induced by the thermal fluctuations of the electrolyte.

  • Details
  • Metrics
Type
research article
DOI
10.1039/c9cp06285h
Web of Science ID

WOS:000537251100006

Author(s)
Scalfi, Laura
Limmer, David T.
Coretti, Alessandro  
Bonella, Sara  
Madden, Paul A.
Salanne, Mathieu
Rotenberg, Benjamin
Date Issued

2020-05-21

Published in
Physical Chemistry Chemical Physics
Volume

22

Issue

19

Start page

10480

End page

10489

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

electrical double-layer

•

ionic liquids

•

thermal agitation

•

water

•

surface

•

energy

•

supercapacitors

•

capacitance

•

performance

•

challenges

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CECAM  
Available on Infoscience
June 18, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/169428
Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés