Connections and performances of Green's function methods for charged and neutral excitations

Abstract

In recent years, Green's function methods have garnered considerable interest due to their ability to target both charged and neutral excitations. Among them, the well-established $GW$ approximation provides accurate ionization potentials and electron affinities and can be extended to neutral excitations using the Bethe-Salpeter equation (BSE) formalism. Here, we investigate the connections between various Green's function methods and evaluate their performance for charged and neutral excitations. Comparisons with other widely-known second-order wave function methods are also reported. Additionally, we calculate the singlet-triplet gap of cycl[3,3,3]azine, a model molecular emitter for thermally activated delayed fluorescence, which has the particularity of having an inverted gap thanks to a substantial contribution from the double excitations. We demonstrate that, within the $GW$ approximation, a second-order BSE kernel with dynamical correction is required to predict this distinctive characteristic.

18 pages, 1 figure

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• Can $GW$ Handle Multireference Systems?
• Anomalous propagators and the particle-particle channel: Hedin's equations
• Anomalous propagators and the particle-particle channel: Bethe-Salpeter equation
• Joint Approximate Diagonalization approach to Quasiparticle Self-Consistent $GW$ calculations
• Analytic $G_0{W}_0$ gradients based on a double-similarity transformation equation-of-motion coupled-cluster treatment
• Excited State Properties from the Bethe--Salpeter Equation: State-to-State Transitions and Spin-Orbit Coupling
• Uncovering relationships between the electronic self-energy and coupled-cluster doubles theory
• Complex Absorbing Potential Green's Function Methods for Resonances
• Diagrammatic theory of the irreducible coupled-cluster self-energy
• Parquet theory for molecular systems: Formalism and static kernel parquet approximation
• Broken symmetry solutions in one-dimensional lattice models via many-body perturbation theory
• Polarizable Continuum Models and Green's Function $\mathbf{GW}$ Formalism: On the Dynamics of the Solvent Electrons
• Optical spectra of small silver clusters with the Bethe-Salpeter formalism: a Reassessment