Issue 8, 2013

Modelling electrified interfaces in quantum chemistry: constant charge vs. constant potential

Abstract

The proper description of electrified metal/solution interfaces, as they occur in electrochemical systems, is a key component for simulating the unique features of electrocatalytic reactions using electronic structure calculations. While in standard solid state (plane wave, periodic boundary conditions) density functional theory (DFT) calculations several models for describing electrochemical environments exist, for cluster models in a quantum chemistry approach (atomic orbital basis, finite system) this is not straightforward. In this work, two different approaches for the theoretical description of electrified interfaces of nanoparticles, the constant charge and the constant potential model, are discussed. Different schemes for describing electrochemical reactions including solvation models are tested for a consistent description of the electrochemical potential and the local chemical behavior for finite structures. The different schemes and models are investigated for the oxygen reduction reaction (ORR) on a hemispherical cuboctahedral platinum nanoparticle.

Graphical abstract: Modelling electrified interfaces in quantum chemistry: constant charge vs. constant potential

Article information

Article type
Paper
Submitted
01 Aug 2012
Accepted
12 Dec 2012
First published
13 Dec 2012

Phys. Chem. Chem. Phys., 2013,15, 2712-2724

Modelling electrified interfaces in quantum chemistry: constant charge vs. constant potential

U. Benedikt, W. B. Schneider and A. A. Auer, Phys. Chem. Chem. Phys., 2013, 15, 2712 DOI: 10.1039/C2CP42675G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements