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Communication: Towards ab initio self-energy embedding theory in quantum chemistry

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4938562· OSTI ID:1843752
 [1];  [2];  [2]
  1. Univ. of Michigan, Ann Arbor, MI (United States); University of Michigan
  2. Univ. of Michigan, Ann Arbor, MI (United States)
+ Show Author Affiliations

The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. Furthermore, these advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.

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:
1843752
Alternate ID(s):
OSTI ID: 22493359
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 143; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (30)

Periodic and fragment models based on the local correlation approach
  • Usvyat, Denis; Maschio, Lorenzo; Schütz, Martin
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 4 https://doi.org/10.1002/wcms.1357
journal January 2018
Embedding Methods in Quantum Chemistry book November 2017
Multiple impurities and combined local density approximations in site-occupation embedding theory journal November 2018
Self-consistent second-order Green’s function perturbation theory for periodic systems journal February 2016
Coupled cluster Green function: Model involving single and double excitations journal April 2016
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
Green’s function coupled cluster formulations utilizing extended inner excitations journal December 2018
Quantum system partitioning at the single-particle level journal November 2018
Explicitly correlated renormalized second-order Green’s function for accurate ionization potentials of closed-shell molecules journal June 2019
An optimized twist angle to find the twist-averaged correlation energy applied to the uniform electron gas journal May 2019
RPA natural orbitals and their application to post-Hartree-Fock electronic structure methods journal December 2019
Local density approximation in site-occupation embedding theory journal May 2016
Properties of advanced coupled-cluster Green's function journal July 2017
Dynamical screening in correlated electron systems—from lattice models to realistic materials journal July 2016
Finite temperature quantum embedding theories for correlated systems journal February 2017
Coupled-cluster Green's function: Analysis of properties originating in the exponential parametrization of the ground-state wave function journal December 2016
Projected site-occupation embedding theory journal July 2019
Site-occupation Green's function embedding theory: A density functional approach to dynamical impurity solvers journal November 2019
Sparse sampling approach to efficient ab initio calculations at finite temperature journal January 2020
Testing self-energy embedding theory in combination with GW journal October 2017
Site-occupation embedding theory using Bethe ansatz local density approximations journal June 2018
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
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
Finite temperature quantum embedding theories for correlated systems 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
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An optimized twist angle to find the twist-averaged correlation energy applied to the uniform electron gas text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical properties
Density functional theory
Density-matrix
Full configuration interaction
Green-functions technique
Interpolation
Magnetism
Perturbation theory
Potential energy surfaces
Quantum chemistry