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

Jun Cheng, Joost VandeVondele

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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
Issue number8
Publication statusPublished - 25 Feb 2016


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