Impact of Solvation on the GW Quasiparticle Spectra of Molecules

Mauro Del Ben, Jacob Clary, Ravishankar Sundararaman, Derek Vigil-Fowler

Research output: Contribution to journalArticlepeer-review

5 Scopus Citations

Abstract

First-principles calculations for electrochemistry require accurate treatment of both electronic structure and solvation. The perturbative GW approximation starting from density functional theory (DFT) calculations accurately models materials systems with varying dimensionality. Continuum solvation models enable efficient treatment of solvation effects in DFT calculations, but their applications with beyond-DFT electronic structure methods such as GW have been limited. Here, we introduce the frequency-dependent liquid polarizability from a nonlocal continuum solvation model in the screened Coulomb interaction of full-frequency GW calculations with a solvated DFT starting point. We show that the liquid screening contributions substantially reduce the HOMO-LUMO gap of molecules by 3-5 eV, while solvent effects on the DFT starting point negligibly impact the GW gap. The resulting framework facilitates the simultaneous electronic and solvation accuracy needed for first-principles electrochemistry.

Original languageAmerican English
Article number085001
Number of pages8
JournalJournal of Applied Physics
Volume134
Issue number8
DOIs
StatePublished - 28 Aug 2023

Bibliographical note

Publisher Copyright:
© 2023 Author(s).

NREL Publication Number

  • NREL/JA-2C00-87461

Keywords

  • density functional theory
  • electrochemistry
  • electronic structure methods
  • electrostatics
  • first-principle calculations
  • GW-approximation
  • HOMO and LUMO
  • implicit solvation
  • polarizability
  • quasiparticle

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