Accurate Ground State Energies of Solids and Molecules from Time Dependent Density Functional Theory

Abstract

We demonstrate that ground state energies approaching chemical accuracy can be obtained by combining the adiabatic connection fluctuation-dissipation theorem (ACFDT) with time-dependent density functional theory (TDDFT). The key ingredient is a renormalization scheme, which eliminates the divergence of the correlation hole characteristic of any local kernel. This new class of renormalized kernels gives a significantly better description of the short-range correlations in covalent bonds compared to the random phase approximation (RPA) and yields a four fold improvement of RPA binding energies in both molecules and solids. We also consider examples of barrier heights in chemical reactions, molecular adsorption and graphene interacting with metal surfaces, which are three examples where RPA has been successful. In these cases, the renormalized kernel provides results that are of equal quality or even slightly better than RPA, with a similar computational cost.

arXiv commentAccepted for publication in Phys. Rev. Lett. Supplementary material included as appendix

References in corpus (11)

• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• Random-phase approximation and its applications in computational chemistry and materials science
• Beyond the Random Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations
• Dispersive and Covalent Interactions Between Graphene and Metal Surfaces from the Random Phase Approximation
• Linear density response function in the projector-augmented wave method: Applications to solids, surfaces, and interfaces
• The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes
• Many-body quantum chemistry for the electron gas: convergent perturbative theories
• Extending the random-phase approximation for electronic correlation energies: The renormalized adiabatic local density approximation
• Beyond the random phase approximation: Improved description of short range correlation by a renormalized adiabatic local density approximation
• Static correlation beyond the random phase approximation: Dissociating H2 with the Bethe-Salpeter equation and time-dependent GW
• Beyond the RPA on the cheap: improved correlation energies with the efficient "Radial Exchange Hole" kernel

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