Dynamical correlation energy of metals in large basis sets from downfolding and composite approaches
James M. Callahan, Malte F. Lange, Timothy C. Berkelbach
Abstract
Coupled-cluster theory with single and double excitations (CCSD) is a promising ab initio method for the electronic structure of three-dimensional metals, for which second-order perturbation theory (MP2) diverges in the thermodynamic limit. However, due to the high cost and poor convergence of CCSD with respect to basis size, applying CCSD to periodic systems often leads to large basis set errors. In a common “composite” method, MP2 is used to recover the missing dynamical correlation energy through a focal-point correction, but the inadequacy of finite-order perturbation theory for metals raises questions about this approach. Here, we describe how high-energy excitations treated by MP2 can be “downfolded” into a low-energy active space to be treated by CCSD. Comparing how the composite and downfolding approaches perform for the uniform electron gas, we find that the latter converges more quickly with respect to the basis set size. Nonetheless, the composite approach is surprisingly accurate because it removes the problematic MP2 treatment of double excitations near the Fermi surface. Using this method to estimate the CCSD correlation energy in the combined complete basis set and thermodynamic limits, we find that CCSD recovers 85%–90% of the exact correlation energy at rs = 4. We also test the composite approach with the direct random-phase approximation used in place of MP2, yielding a method that is typically (but not always) more cost effective due to the smaller number of orbitals that need to be included in the more expensive CCSD calculation.