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Rigorous Ab Initio Quantum Embedding for Quantum Chemistry Using Green’s Function Theory: Screened Interaction, Nonlocal Self-Energy Relaxation, Orbital Basis, and Chemical Accuracy

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [2]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry. Dept. of Physics; DOE/OSTI
  2. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
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We present a detailed discussion of the 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 level. We apply SEET to molecular examples where our chosen subsystem is made out of a set of strongly correlated orbitals while the weakly correlated orbitals constitute an environment. Consequently, a highly accurate method is used to calculate the self-energy for the system, while a lower-level method is employed to find the self-energy for the environment. Such a self-energy separation is very general, and to make the SEET 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 of 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 wave function quantum chemistry methods.

Research Organization:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0010381
OSTI ID:
1534553
Alternate ID(s):
OSTI ID: 1843755
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 12; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (20)

Quantum simulations of materials on near-term quantum computers journal July 2020
First-principles studies of strongly correlated states in defect spin qubits in diamond journal January 2020
Projection based embedding theory for solving Kohn-Sham density functional theory preprint January 2018
Embedding Methods in Quantum Chemistry book November 2017
Exploring connections between statistical mechanics and Green’s functions for realistic systems: Temperature dependent electronic entropy and internal energy from a self-consistent second-order Green’s function journal November 2016
Comparison of Green’s functions for transition metal atoms using self-energy functional theory and coupled-cluster singles and doubles (CCSD) journal June 2018
Finite temperature quantum embedding theories for correlated systems journal February 2017
Projected site-occupation embedding theory journal July 2019
Density functional theory plus dynamical mean-field theory with natural atomic orbital projectors journal September 2019
Charge ordering and correlation effects in the extended Hubbard model journal March 2017
Testing self-energy embedding theory in combination with GW journal October 2017
Dynamical configuration interaction: Quantum embedding that combines wave functions and Green's functions journal March 2019
Towards the Solution of the Many-Electron Problem in Real Materials: Equation of State of the Hydrogen Chain with State-of-the-Art Many-Body Methods journal September 2017
To the Theory of Inhomogeneous Electron Gas journal August 2018
Exploring connections between statistical mechanics and Green's functions for realistic systems. Temperature dependent electronic entropy and internal energy from a self-consistent second-order Green's function text January 2016
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Charge ordering and correlation effects in the extended Hubbard model text January 2016
Towards the solution of the many-electron problem in real materials: equation of state of the hydrogen chain with state-of-the-art many-body methods text January 2017
Comparison of Green's functions for transition metal atoms using self-energy functional theory and coupled-cluster singles and doubles (CCSD) text January 2018
Dynamical configuration interaction: Quantum embedding that combines wave functions and Green's functions text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Hamiltonians
chemical calculations
energy
hybridization
impurities