Effective Hamiltonians for the study of real metals using quantum chemical theories

Abstract

Computationally efficient and accurate quantum mechanical approximations to solve the many-electron Schrödinger equation are at the heart of computational materials science. In that respect the coupled cluster hierarchy of methods plays a central role in molecular quantum chemistry because of its systematic improvability and computational efficiency. In this hierarchy, coupled cluster singles and doubles (CCSD) is one of the most important steps in moving towards chemical accuracy and, in recent years, its scope has successfully been expanded to the study of insulating surfaces and solids. Here, we show that CCSD theory can also be applied to real metals. In so doing, we overcome the limitation of needing extremely large supercells to capture long range electronic correlation effects. An effective Hamiltonian can be found using the transition structure factor--a map of electronic excitations from the Hartree--Fock wavefunction--which has fewer finite size effects than conventional periodic boundary conditions. This not only paves the way of applying coupled cluster methods to real metals but also reduces the computational cost by two orders of magnitude compared to previous methods. Our applications to phases of lithium and silicon show a resounding success in reaching the thermodynamic limit, taking the first step towards a truly universal quantum chemical treatment of solids.

arXiv comment8 pages, 4 figures, 1 table

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