title: Calculation of Electrochemical Energy Levels in Water Using the Random Phase Approximation and a Double Hybrid Functional.
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.
authors.affiliation: 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.
authors.forename: Jun
authors.initials: J
authors.lastname: Cheng
authors.affiliation: Department of Materials, ETH Zurich, Wolfgang-Pauli-Strasse 27, CH-8093 Zurich, Switzerland.
authors.forename: Joost
authors.initials: J
authors.lastname: VandeVondele