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

Jun Cheng, Joost VandeVondele

Research output: Contribution to journalArticle

15 Citations (Scopus)

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.

Original languageEnglish
Article number086402
JournalPhysical Review Letters
Volume116
Issue number8
DOIs
Publication statusPublished - 25 Feb 2016

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