Accurate and Efficient Prediction of Double Excitation Energies Using the Particle-Particle Random Phase Approximation

Abstract

Double excitations are crucial to understanding numerous chemical, physical, and biological processes, but accurately predicting them remains a challenge. In this work, we explore the particle-particle random phase approximation (ppRPA) as an efficient and accurate approach for computing double excitation energies. We benchmark ppRPA using various exchange-correlation functionals for 21 molecular systems and two point defect systems. Our results show that ppRPA with functionals containing appropriate amounts of exact exchange provides accuracy comparable to high-level wave function methods such as CCSDT and CASPT2, with significantly reduced computational cost. Furthermore, we demonstrate the use of ppRPA starting from an excited ($N-2$)-electron state calculated by $\Delta$SCF for the first time, as well as its application to double excitations in bulk periodic systems. These findings suggest that ppRPA is a promising tool for the efficient calculation of double and partial double excitation energies in both molecular and bulk systems.

References in corpus (16)

• The Bethe-Salpeter Equation Formalism: From Physics to Chemistry
• Excited states using semistochastic heat-bath configuration interaction
• Excited state properties of point defects in semiconductors and insulators investigated with time-dependent density functional theory
• 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
• Full-frequency dynamical Bethe-Salpeter equation without frequency and a study of double excitations
• Weight Dependence of Local Exchange-Correlation Functionals in Ensemble Density-Functional Theory: Double Excitations in Two-Electron Systems
• A Mountaineering Strategy to Excited States: Revising Reference Values with EOM-CC4
• How accurate are EOM-CC4 vertical excitation energies?
• State-Specific Coupled-Cluster Methods for Excited States
• The three channels of many-body perturbation theory: $GW$, particle-particle, and electron-hole $T$-matrix self-energies
• Comparing particle-particle and particle-hole channels of random-phase approximation
• Linear Scaling Calculations of Excitation Energies with Active-Space Particle-Particle Random Phase Approximation
• Multireference Density Functional Theory for Describing Ground and Excited States with Renormalized Singles
• Accurate Excitation Energies of Point Defects from Fast Particle-Particle Random Approximation Calculations
• Anomalous propagators and the particle-particle channel: Hedin's equations

Cited by in corpus (3)

• Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics
• The QUEST Database of Highly-Accurate Excitation Energies
• LibppRPA: An Open-Source Library for Particle-Particle Random Phase Approximation