Dynamical Correction to the Bethe-Salpeter Equation Beyond the Plasmon-Pole Approximation

Abstract

The Bethe-Salpeter equation (BSE) formalism is a computationally affordable method for the calculation of accurate optical excitation energies in molecular systems. Similar to the ubiquitous adiabatic approximation of time-dependent density-functional theory, the static approximation, which substitutes a dynamical (i.e., frequency-dependent) kernel by its static limit, is usually enforced in most implementations of the BSE formalism. Here, going beyond the static approximation, we compute the dynamical correction of the electron-hole screening for molecular excitation energies thanks to a renormalized first-order perturbative correction to the static BSE excitation energies. The present dynamical correction goes beyond the plasmon-pole approximation as the dynamical screening of the Coulomb interaction is computed exactly within the random-phase approximation. Our calculations are benchmarked against high-level (coupled-cluster) calculations, allowing to assess the clear improvement brought by the dynamical correction for both singlet and triplet optical transitions.

arXiv comment12 pages, 2 figures

References in corpus (24)

• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks
• A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules
• Perspectives on double-excitations in TDDFT
• Reference Energies for Double Excitations
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• First-principles GW calculations for DNA and RNA nucleobases
• Quasi-Particle Self-Consistent $GW$ for Molecules
• Conserving approximations in time-dependent quantum transport: Initial correlations and memory effects
• An assessment of the low-lying excitation energies and triplet instabilities of organic molecules with an ab initio Bethe-Salpeter equation approach
• A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Exotic Molecules and Radicals
• Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
• Assessment of Dressed Time-Dependent Density-Functional Theory for the Low-Lying Valence States of 28 Organic Chromophores
• Ab Initio Bethe-Salpeter Equation Approach to Neutral Excitations in Molecules with Numeric Atom-Centered Orbitals
• Evaluating 0-0 Energies with Theoretical Tools: a Short Review
• Separable Resolution-of-the-Identity with All-Electron Gaussian Bases: Application to Cubic-scaling RPA
• Unphysical Discontinuities in GW Methods
• Green functions and self-consistency: insights from the spherium model
• Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?
• Time-dependent density-functional and reduced density-matrix methods for few electrons: Exact versus adiabatic approximations
• Range-separated time-dependent density-functional theory with a frequency-dependent second-order Bethe-Salpeter correlation kernel
• Kadanoff-Baym approach to double-excitations in finite systems
• Dynamical Kernels for Optical Excitations
• A formally exact one-frequency-only Bethe-Salpeter-like equation. Similarities and differences between GW +BSE and self-consistent RPA

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