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Impact of solvation on the GW quasiparticle spectra of molecules

Journal Article · · Journal of Applied Physics
DOI:https://doi.org/10.1063/5.0160173· OSTI ID:2000012
 [1];  [2];  [3];  [1]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  3. Rensselaer Polytechnic Institute, Troy, NY (United States)
+ Show Author Affiliations
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. In this study, 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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC36-08GO28308; SC0022247
OSTI ID:
2000012
Report Number(s):
NREL/JA--2C00-87461; MainId:88236; UUID:4619736c-4019-4636-9b8d-b8dae9701269; MainAdminID:70576
Journal Information:
Journal of Applied Physics, Journal Name: Journal of Applied Physics Journal Issue: 8 Vol. 134; ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (68)

Density Functional Theory for Battery Materials journal September 2019
Electronic properties of interfaces and defects from many-body perturbation theory: Recent developments and applications journal January 2011
On the description of the environment polarization response to electronic transitions journal September 2018
The Dielectric Function for Water and Its Application to van der Waals Forces journal November 2000
The dielectric relaxation of water between 0°C and 35°C journal June 1999
On the electronic structure of liquid water: Facts and reflections journal October 1997
BerkeleyGW: A massively parallel computer package for the calculation of the quasiparticle and optical properties of materials and nanostructures journal June 2012
Optimization algorithm for the generation of ONCV pseudopotentials journal November 2015
Large-scale GW calculations on pre-exascale HPC systems journal February 2019
First-principles computational electrochemistry: Achievements and challenges journal December 2012
JDFTx: Software for joint density-functional theory journal January 2017
Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface journal May 2022
GW 100: Benchmarking G 0 W 0 for Molecular Systems journal November 2015
Accurate Prediction of the S1 Excitation Energy in Solvated Azobenzene Derivatives via Embedded Orbital-Tuned Bethe-Salpeter Calculations journal February 2020
GW Quasiparticle Energies and Bandgaps of Two-Dimensional Materials Immersed in Water journal August 2022
Spatial Decay and Limits of Quantum Solute–Solvent Interactions journal March 2023
Combining the Many-Body GW Formalism with Classical Polarizable Models: Insights on the Electronic Structure of Molecular Solids journal June 2016
Electronic Levels of Excess Electrons in Liquid Water journal April 2017
Absolute Energy Levels of Liquid Water journal May 2018
Benchmarking the Starting Points of the GW Approximation for Molecules journal December 2012
Electron Binding Energies of Hydrated H 3 O + and OH - :  Photoelectron Spectroscopy of Aqueous Acid and Base Solutions Combined with Electronic Structure Calculations journal March 2006
Photoelectron Spectra of Aqueous Solutions from First Principles journal May 2016
Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation journal April 2004
First-Principle Protocol for Calculating Ionization Energies and Redox Potentials of Solvated Molecules and Ions: Theory and Application to Aqueous Phenol and Phenolate journal May 2012
Electron affinity of liquid water journal January 2018
Many-body screening effects in liquid water journal May 2023
Monolayer MoS2 Bandgap Modulation by Dielectric Environments and Tunable Bandgap Transistors journal July 2016
High-resolution soft X-ray photoelectron spectroscopy of liquid water journal January 2011
Recent theoretical progress in the development of photoanode materials for solar water splitting photoelectrochemical cells journal January 2015
Energy level alignment at semiconductor–water interfaces from atomistic and continuum solvation models journal January 2017
The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features journal January 2018
Accurate vertical ionization energy and work function determinations of liquid water and aqueous solutions journal January 2021
Influence of the exchange screening parameter on the performance of screened hybrid functionals journal December 2006
Zero-kinetic-energy photoelectron spectroscopy of the hydrogen-bonded phenol-water complex journal July 1994
A recipe for free-energy functionals of polarizable molecular fluids journal April 2014
Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X − journal May 2014
Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz journal February 2015
The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model journal February 2015
Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach journal April 2016
Efficient treatment of molecular excitations in the liquid phase environment via stochastic many-body theory journal August 2021
The GW method journal March 1998
Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 and GW with numeric atom-centered orbital basis functions journal May 2012
Theory of Many-Particle Systems. I journal September 1959
Quantum Theory of the Dielectric Constant in Real Solids journal April 1962
Dielectric Constant with Local Field Effects Included journal January 1963
New Method for Calculating the One-Particle Green's Function with Application to the Electron-Gas Problem journal August 1965
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Dynamical aspects of correlation corrections in a covalent crystal journal February 1982
Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies journal October 1986
Self-energy operators and exchange-correlation potentials in semiconductors journal June 1988
GW approach to the calculation of electron self-energies in semiconductors journal October 1988
Ab initioGWquasiparticle energies of small sodium clusters by an all-electron mixed-basis approach journal March 2001
Optical excitations in organic molecules, clusters, and defects studied by first-principles Green’s function methods journal May 2006
Joint density-functional theory for electronic structure of solvated systems journal May 2007
Self-consistent G W calculations for semiconductors and insulators journal June 2007
Fully self-consistent GW calculations for molecules journal February 2010
Electronic excitations from a perturbative LDA + G d W approach journal November 2010
First-principles GW calculations for DNA and RNA nucleobases journal March 2011
Regularization of the Coulomb singularity in exact exchange by Wigner-Seitz truncated interactions: Towards chemical accuracy in nontrivial systems journal April 2013
Local field effects and the dielectric response matrix of insulators: A model journal May 1974
Excitation spectra of aromatic molecules within a real-space G W -BSE formalism: Role of self-consistency and vertex corrections journal August 2016
Static subspace approximation for the evaluation of G 0 W 0 quasiparticle energies within a sum-over-bands approach journal March 2019
First-Principles Calculations of Quasiparticle Excitations of Open-Shell Condensed Matter Systems journal July 2012
Electronic Properties of Liquid Water in the Vacuum Ultraviolet journal July 1968
Generalized Gradient Approximation Made Simple journal October 1996
Band gaps of liquid water and hexagonal ice through advanced electronic-structure calculations journal June 2021
Electronic excitations: density-functional versus many-body Green’s-function approaches journal June 2002
The GW Miracle in Many-Body Perturbation Theory for the Ionization Potential of Molecules journal December 2021

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
GW-approximation
HOMO and LUMO
density functional theory
electrochemistry
electronic structure methods
electrostatics
first-principle calculations
implicit solvation
polarizability
quasiparticle