The electrochemical environment strongly influences charge states of intermediate species and plays a critical role in the pathways of electro-catalytic processes. Direct first-principles calculations of the electrochemical systems are computationally intensive because of the need for thermodynamic sampling of liquid and electrolyte configurations. Continuum solvation methods facilitate rapid first-principles prediction of structures and reaction energetics at solid-liquid interfaces, but prediction of corresponding excited state properties and energetics beyond the density-functional level remains challenging. We combine continuum solvation models derived in the framework of joint density-functional theory (JDFT) with GW and RPA many-body calculations, implemented in an open-source interface between the JDFTx and BerkeleyGW softwares. We predict the shift in excitations of various solutes due to aqueous environments and find that the liquid contribution to the screened Coulomb interaction dominates in comparison to the modification of the one-electron potential. This technique will facilitate correlated energy calculations and first-principles spectroscopy, substantially expanding the toolkit of \emph{ab initio} electro-catalysis.

Excited states in liquid environments with GW and continuum models

2019 Spring National Meeting

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