Averting the infrared catastrophe in the gold standard of quantum chemistry

Abstract

Coupled-cluster theories can be used to compute ab initio electronic correlation energies of real materials with systematically improvable accuracy. However, the widely-used coupled cluster singles and doubles plus perturbative triples (CCSD(T)) method is only applicable to insulating materials. For zero-gap materials the truncation of the underlying many-body perturbation expansion leads to an infrared catastrophe. Here, we present a novel perturbative triples formalism that yields convergent correlation energies in metallic systems. Furthermore, the computed correlation energies for the three dimensional uniform electron gas at metallic densities are in good agreement with quantum Monte Carlo results. At the same time the newly proposed method retains all desirable properties of CCSD(T) such as its accuracy for insulating systems as well as its low computational cost compared to a full inclusion of the triples. This paves the way for ab initio calculations of real metals with chemical accuracy.

6 pages, 1 figure, 1 table plus a supplemental material of 14 pages, 4 figures and 1 table

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Cited by in corpus (14)

• How accurate are simulations and experiments for the lattice energies of molecular crystals?
• Adsorption and Vibrational Spectroscopy of CO on the Surface of MgO from Periodic Local Coupled-Cluster Theory
• Periodic Local Coupled-Cluster Theory for Insulators and Metals
• Another Angle on Benchmarking Noncovalent Interactions
• Unveiling Intrinsic Many-Body Complexity by Compressing Single-Body Triviality
• Post-CCSD(T) corrections in the S66 noncovalent interactions benchmark
• Systematic discrepancies between reference methods for non-covalent interactions within the S66 dataset
• Understanding Discrepancies of Wavefunction Theories for Large Molecules
• Finite-size Effects in periodic EOM-CCSD for Ionization Energies and Electron Affinities: Convergence Rate and Extrapolation to the Thermodynamic Limit
• Self-Refinement of Auxiliary-Field Quantum Monte Carlo via Non-Orthogonal Configuration Interaction
• Efficient Implementation of the Random Phase Approximation with Domain-based Local Pair Natural Orbitals
• Ground-States for Metals from Converged Coupled Cluster Calculations
• Excited States of the Uniform Electron Gas
• Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory