Beyond the Random Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations

Abstract

The random phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange energy, represents the state-of-the-art exchange-correlation functional within density-functional theory (DFT). However, the standard RPA practice -- evaluating both the exact-exchange and the RPA correlation energy using local or semilocal Kohn-Sham (KS) orbitals -- leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior is largely corrected by adding a "single excitation" (SE) contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent exact-exchange total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using Kohn-Sham orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of non-covalent intermolecular interactions.

5 pages, 4 figures, and an additional supplementary material

References in corpus (6)

• The Ground State Correlation Energy of the Random Phase Approximation from a Ring Coupled Cluster Doubles Approach
• Adiabatic-connection fluctuation-dissipation density-functional theory based on range separation
• First-Principle Description of Correlation Effects in Layered Materials
• Long-range-corrected hybrids including RPA correlation
• Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions
• Random-phase-approximation-based correlation energy functionals: Benchmark results for atoms

Cited by in corpus (63)

• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• van der Waals forces in density functional theory: The vdW-DF method
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• Long-range correlation energy calculated from coupled atomic response functions
• Random-phase approximation and its applications in computational chemistry and materials science
• Graphite and Hexagonal Boron-Nitride Possess the Same Interlayer Distance. Why?
• Dispersive and Covalent Interactions Between Graphene and Metal Surfaces from the Random Phase Approximation
• Assessment of correlation energies based on the random-phase approximation
• Interatomic Methods for the Dispersion Energy Derived from the Adiabatic Connection Fluctuation-Dissipation Theorem
• Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory
• The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes
• On the physisorption of water on graphene: Sub-chemical accuracy from many-body electronic structure methods
• Correlation energy expressions from the adiabatic-connection fluctuation-dissipation theorem approach
• Exchange-Correlation Energy from Pairing Matrix Fluctuation and the Particle-Particle Random Phase Approximation
• Bond Breaking and Bond Formation: How Electron Correlation is Captured in Many-Body Perturbation Theory and Density-Functional Theory
• Fast and accurate quantum Monte Carlo for molecular crystals
• Closed-shell ring coupled cluster doubles theory with range separation applied on weak intermolecular interactions
• Correlation energy for the homogeneous electron gas: exact Bethe-Salpeter solution and new approximate evaluation
• Correlation potentials for molecular bond dissociation within the self-consistent random phase approximation
• Stability and metastability of clusters in a reactive atmosphere: theoretical evidence for unexpected stoichiometries of MgMOx
• Many-body dispersion effects in the binding of adsorbates on metal surfaces
• Extending the random-phase approximation for electronic correlation energies: The renormalized adiabatic local density approximation
• Properties of the water to boron nitride interaction: from zero to two dimensions with benchmark accuracy
• Accurate Ground State Energies of Solids and Molecules from Time Dependent Density Functional Theory
• Surface Energetics of Alkaline-Earth Metal Oxides: Trends in Stability and Adsorption of Small Molecules
• Accurate ground state- and quasiparticle energies: beyond the RPA and GW methods with adiabatic exchange-correlation kernels
• The random phase approximation applied to ice
• Singles correlation energy contributions in solids
• Correlation energy within exact-exchange ACFD theory: systematic development and simple approximations
• Orbital-dependent second-order scaled-opposite-spin correlation functionals in the optimized effective potential method
• Benchmarking van der Waals Density Functionals with Experimental Data: Potential Energy Curves for H2 Molecules on Cu(111), (100), and (110) Surfaces
• Lattice energies of molecular solids from the random phase approximation with singles corrections
• Renormalized Singles Green's Function in the T-Matrix Approximation for Accurate Quasiparticle Energy Calculation
• Towards efficient orbital-dependent density functionals for weak and strong correlation
• Assessing the performance of the Random Phase Approximation for exchange and superexchange coupling constants in magnetic crystalline solids
• Efficient and accurate description of adsorption in zeolites
• Analytical Energy Gradients in Range-Separated Hybrid Density Functional Theory with Random Phase Approximation
• Molecular bonding with the RPAx: from weak dispersion forces to strong correlation
• Accuracy of basis-set extrapolation schemes for DFT-RPA correlation energies in molecular calculations
• Test set for materials science and engineering with user-friendly graphic tools for error analysis: Systematic benchmark of the numerical and intrinsic errors in state-of-the-art electronic-structure approximations
• Comparing particle-particle and particle-hole channels of random-phase approximation
• Multireference Density Functional Theory for Describing Ground and Excited States with Renormalized Singles
• Assessment of the second-order statically screened exchange correction to the random phase approximation for correlation energies
• Wave-function inspired density functional applied to the H${}_2$/H${}_2^{+}$ challenge
• Random Phase Approximation Applied to Many-Body Noncovalent Systems
• A route to improving RPA excitation energies through its connection to equation-of-motion coupled cluster theory
• Combining Renormalized Singles $GW$ Methods with the Bethe-Salpeter Equation for Accurate Neutral Excitation Energies
• Renormalized Singles with Correlation in $GW$ Green's Function Theory for Accurate Quasiparticle Energies
• Correlated excited states in the narrow gap band semiconductor FeSi and antiferromagnetic screening of local spin moments
• Assessment of random-phase approximation and second order Møller-Plesset perturbation theory for many-body interactions in solid ethane, ethylene, and acetylene
• DFT-D Investigation of the Interaction Between Ir(III) Based Photosensitizers and Small Silver Clusters Ag${}_n$ ($n$=2-20, 92)
• Tensor hypercontraction for fully self-consistent imaginary-time GF2 and GWSOX methods: theory, implementation, and role of the Green's function second-order exchange for intermolecular interactions
• Phase Stability of the Argon Crystal: A First-Principles Study Based on Random Phase Approximation plus Renormalized Single Excitation Corrections
• Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and Projector Augmented-wave methods
• Generalized many-body perturbation theory for the electron correlation energy: multi-reference random phase approximation via diagrammatic resummation
• Understanding the wetting of transition metal dichalcogenides from an ab initio perspective
• Regularized Perturbation Theory for Ab initio Solids
• Competing charge density wave and antiferromagnetism of metallic atom wires in GaN(10$\overline{1}$0) and ZnO(10$\overline{1}$0)
• Benchmarking the accuracy of the separable resolution of the identity approach for correlated methods in the numeric atom-centered orbitals framework
• Comment on "Quasi-One-Dimensional Metal-Insulator Transitions in Compound Semiconductor Surfaces"
• Bayesian approach to electron correlation in density functional theory
• Homogeneous electron gas in arbitrary dimensions
• Coulomb Interactions between Dipolar Quantum Fluctuations in van der Waals Bound Molecules and Materials