Combining Renormalized Singles $GW$ Methods with the Bethe-Salpeter Equation for Accurate Neutral Excitation Energies

Abstract

We apply the renormalized singles (RS) Green's function in the Bethe-Salpeter equation (BSE)/$GW$ approach to predict accurate neutral excitation energies of molecular systems. The BSE calculations are performed on top of the $G_{\text{RS}}{W}_{\text{RS}}$ method, which uses the RS Green's function also for the computation of the screened Coulomb interaction $W$. We show that the BSE/$G_{\text{RS}}{W}_{\text{RS}}$ approach significantly outperforms BSE/$G_0{W}_0$ for predicting excitation energies of valence, Rydberg and charge transfer (CT) excitations by benchmarking the Truhlar-Gagliardi set, Stein CT set and an atomic Rydberg test set. For the Truhlar-Gagliardi test set, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ provides comparable accuracy to time-dependent density functional theory (TDDFT) and is slightly better than BSE starting from eigenvalue self-consistent $GW$ (ev$GW$). For the Stein CT test set, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ significantly outperforms BSE/$G_0{W}_0$ and TDDFT with the accuracy comparable to BSE/ev$GW$. We also show that BSE/$G_{\text{RS}}{W}_{\text{RS}}$ predicts Rydberg excitation energies of atomic systems well. Besides the excellent accuracy, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ largely eliminates the dependence on the choice of the density functional approximation. This work demonstrates that the BSE/$G_{\text{RS}}{W}_{\text{RS}}$ approach is accurate and efficient for predicting excitation energies for a broad range of systems, which expands the applicability of the BSE/$GW$ approach.

References in corpus (36)

• Quasiparticle Self-Consistent GW Theory
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• Beyond the Random Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations
• Orbital Optimized Density Functional Theory for Electronic Excited States
• Unified description of ground and excited states of finite systems: the self-consistent GW approach
• The Bethe-Salpeter Equation Formalism: From Physics to Chemistry
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• Self-consistent GW: All-electron implementation with localized basis functions
• Assessment of correlation energies based on the random-phase approximation
• Localized Orbital Scaling Correction for Systematic Elimination of Delocalization Error in Density Functional Approximations
• Quasi-Particle Self-Consistent $GW$ for Molecules
• QUESTDB: a database of highly-accurate excitation energies for the electronic structure community
• Towards GW Calculations on Thousands of Atoms
• Exciton band structure in two-dimensional materials
• Reference Energies for Intramolecular Charge-Transfer Excitations
• Short to long-range charge-transfer excitations in the zincbacteriochlorin-bacteriochlorin complex: a Bethe-Salpeter study
• Cubic-scaling all-electron GW calculations with a separable density-fitting space-time approach
• Low-order Scaling $G_0{W}_0$ by Pair Atomic Density Fitting
• Low-scaling $GW$ with benchmark accuracy and application to phosphorene nanosheets
• Ab Initio Bethe-Salpeter Equation Approach to Neutral Excitations in Molecules with Numeric Atom-Centered Orbitals
• Efficient ab initio calculations of bound and continuum excitons
• Many-body Green's function GW and Bethe-Salpeter study of the optical excitations in a paradigmatic model dipeptide
• Unphysical Discontinuities in GW Methods
• Green functions and self-consistency: insights from the spherium model
• Renormalized Singles Green's Function in the T-Matrix Approximation for Accurate Quasiparticle Energy Calculation
• Dynamical Correction to the Bethe-Salpeter Equation Beyond the Plasmon-Pole Approximation
• Koopmans Meets Bethe-Salpeter: Excitonic Optical Spectra without GW
• Spin-Conserved and Spin-Flip Optical Excitations From the Bethe-Salpeter Equation Formalism
• Unphysical Discontinuities, Intruder States and Regularization in $GW$ Methods
• Static and Dynamic Bethe-Salpeter Equations in the $T$-Matrix Approximation
• A quantum embedding theory in the screened Coulomb interaction: Combining configuration interaction with GW/BSE
• Modelling the photochrome-TiO2 interface with Bethe-Salpeter and TD-DFT methods
• Multireference Density Functional Theory for Describing Ground and Excited States with Renormalized Singles
• Combining Localized Orbital Scaling Correction and Bethe-Salpeter Equation for Accurate Excitation Energies
• Renormalized Singles with Correlation in $GW$ Green's Function Theory for Accurate Quasiparticle Energies

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