Rigorous ab initio quantum embedding for quantum chemistry using Green's function theory: screened interaction, non-local self-energy relaxation, orbital basis, and chemical accuracy

Abstract

We present a detailed discussion of self-energy embedding theory (SEET) which is a quantum embedding scheme allowing us to describe a chosen subsystem very accurately while keeping the description of the environment at a lower cost. We apply SEET to molecular examples where commonly our chosen subsystem is made out of a set of strongly correlated orbitals while the weakly correlated orbitals constitute an environment. Such a self-energy separation is very general and to make this procedure applicable to multiple systems a detailed and practical procedure for the evaluation of the system and environment self-energy is necessary. We list all the intricacies for one of the possible procedures while focusing our discussion on many practical implementation aspects such as the choice of best orbital basis, impurity solver, and many steps necessary to reach chemical accuracy. Finally, on a set of carefully chosen molecular examples, we demonstrate that SEET which is a controlled, systematically improvable Green's function method can be as accurate as established wavefunction quantum chemistry methods.

References in corpus (11)

• Continuous-time Monte Carlo methods for quantum impurity models
• Hybridization expansion impurity solver: General formulation and application to Kondo lattice and two-orbital models
• A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry
• Continuous-time auxiliary field Monte Carlo for quantum impurity models
• Multireference Correlation in Long Molecules with the Quadratic Scaling Density Matrix Renormalization Group
• Truncated Configuration Interaction expansions as solvers for correlated quantum impurity models and dynamical mean field theory
• Combined GW and dynamical mean field theory: Dynamical screening effects in transition metal oxides
• Sub-matrix updates for the Continuous-Time Auxiliary Field algorithm
• Systematically improvable multi-scale solver for correlated electron systems
• On the dangers of partial diagrammatic summations: Benchmarks for the two-dimensional Hubbard model in the weak-coupling regime
• Dynamical Mean-Field Theory for Quantum Chemistry

Cited by in corpus (2)

• Finite temperature quantum embedding theories for correlated systems
• Testing self-energy embedding theory in combination with GW