Calculation of Electrochemical Energy Levels in Water Using the Random Phase Approximation and a Double Hybrid Functional

Jun Cheng and Joost VandeVondele
Phys. Rev. Lett. 116, 086402 – Published 25 February 2016
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Abstract

Understanding charge transfer at electrochemical interfaces requires consistent treatment of electronic energy levels in solids and in water at the same level of the electronic structure theory. Using density-functional-theory-based molecular dynamics and thermodynamic integration, the free energy levels of six redox couples in water are calculated at the level of the random phase approximation and a double hybrid density functional. The redox levels, together with the water band positions, are aligned against a computational standard hydrogen electrode, allowing for critical analysis of errors compared to the experiment. It is encouraging that both methods offer a good description of the electronic structures of the solutes and water, showing promise for a full treatment of electrochemical interfaces.

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  • Received 28 August 2015

DOI:https://doi.org/10.1103/PhysRevLett.116.086402

© 2016 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied PhysicsInterdisciplinary Physics

Authors & Affiliations

Jun Cheng*

  • Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People’s Republic of China and Department of Chemistry, University of Aberdeen, Aberdeen AB24 3UE, United Kingdom

Joost VandeVondele

  • Department of Materials, ETH Zurich, Wolfgang-Pauli-Strasse 27, CH-8093 Zurich, Switzerland

  • *chengjun@xmu.edu.cn; jcheng@abdn.ac.uk
  • joost.vandevondele@mat.ethz.ch

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Issue

Vol. 116, Iss. 8 — 26 February 2016

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