Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and Projector Augmented-wave methods

Abstract

The direct random-phase approximation (dRPA) is used to calculate and compare atomization energies for the HEAT set and 10 selected molecules of the G2-1 set using both plane waves and Gaussian-type orbitals. We describe detailed procedures to obtain highly accurate and well converged results for the projector augmented-wave (PAW) method as implemented in the Vienna Ab-initio Simulation Package (VASP) as well as the explicitly correlated dRPA-F12 method as implemented in the TURBOMOLE package. The two approaches agree within chemical accuracy (1 kcal/mol) for the atomization energies of all considered molecules, both for the exact exchange as well as for the dRPA. The root mean-square deviation is 0.41 kcal/mol for the exact exchange (evaluated using density functional theory orbitals) and 0.33 kcal/mol for exact exchange plus the random-phase approximation.

16 pages, 2 figures

References in corpus (14)

• 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
• Predictive GW calculations using plane waves and pseudopotentials
• The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes
• Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory
• Coupled cluster theory in materials science
• Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit
• Bond Breaking and Bond Formation: How Electron Correlation is Captured in Many-Body Perturbation Theory and Density-Functional Theory
• Assessing density functionals using many body theory for hybrid perovskites
• Static correlation and electron localization in molecular dimers from the self-consistent RPA and GW approximation
• Accurate Ground State Energies of Solids and Molecules from Time Dependent Density Functional Theory
• The random phase approximation applied to ice
• Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation
• Cerium Oxides without $U$: The Role of Many-Electron Correlation