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.

arXiv comment6 pages, 1 figure, 1 table plus a supplemental material of 14 pages, 4 figures and 1 table

References in corpus (21)

• Twist-averaged Boundary Conditions in Continuum Quantum Monte Carlo
• The Ground State Correlation Energy of the Random Phase Approximation from a Ring Coupled Cluster Doubles Approach
• Inhomogeneous backflow transformations in quantum Monte Carlo calculations
• Finite-size errors in continuum quantum Monte Carlo calculations
• Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods
• Convergence of many-body wavefunction expansions using a plane wave basis: from the homogeneous electron gas to the solid state
• Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit
• Many-body quantum chemistry for the electron gas: convergent perturbative theories
• Low rank factorization of the Coulomb integrals for periodic coupled cluster theory
• Benchmark all-electron ab initio quantum Monte Carlo calculations for small molecules
• Local embedding of Coupled Cluster theory into the Random Phase Approximation using plane-waves
• Coupled Cluster Channels in the Homogeneous Electron Gas
• Hydrogen dissociation on the Mg(0001) surface from quantum Monte Carlo calculations
• Ab-initio calculations of carbon and boron nitride allotropes and their structural phase transitions using periodic coupled cluster theory
• A periodic equation-of-motion coupled-cluster implementation applied to $F$-centers in alkaline earth oxides
• Effective Hamiltonians for the study of real metals using quantum chemical theories
• A study of the dense Uniform Electron Gas with high orders of Coupled Cluster
• Surface science using coupled cluster theory via local Wannier functions and in-RPA-embedding: the case of water on graphitic carbon nitride
• On the duality of ring and ladder diagrams and its importance for many-electron perturbation theories
• Focal-point approach with pair-specific cusp correction for coupled-cluster theory
• Machine learning for a finite size correction in periodic coupled cluster theory calculations

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