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Title: 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 Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4967449· OSTI ID:1535288
 [1]; ORCiD logo [1];  [1]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
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Including finite-temperature effects from the electronic degrees of freedom in electronic structure calculations of semiconductors and metals is desired; however, in practice it remains exceedingly difficult when using zero-temperature methods, since these methods require an explicit evaluation of multiple excited states in order to account for any finite-temperature effects. Using a Matsubara Green’s function formalism remains a viable alternative, since in this formalism it is easier to include thermal effects and to connect the dynamic quantities such as the self-energy with static thermodynamic quantities such as the Helmholtz energy, entropy, and internal energy. However, despite the promising properties of this formalism, little is known about the multiple solutions of the non-linear equations present in the self-consistent Matsubara formalism and only a few cases involving a full Coulomb Hamiltonian were investigated in the past. Here, to shed some light onto the iterative nature of the Green’s function solutions, we self-consistently evaluate the thermodynamic quantities for a one-dimensional (1D) hydrogen solid at various interatomic separations and temperatures using the self-energy approximated to second-order (GF2). At many points in the phase diagram of this system, multiple phases such as a metal and an insulator exist, and we are able to determine the most stable phase from the analysis of Helmholtz energies. Additionally, we show the evolution of the spectrum of 1D boron nitride to demonstrate that GF2 is capable of qualitatively describing the temperature effects influencing the size of the band gap.

Research Organization:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0010381; ER16391
OSTI ID:
1535288
Alternate ID(s):
OSTI ID: 1333351; OSTI ID: 1843756
Journal Information:
Journal of Chemical Physics, Vol. 145, Issue 20; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 42 works
Citation information provided by
Web of Science

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Cited By (12)

Ground state properties of 3d metals from self-consistent GW approach journal October 2017
Finite temperature quantum embedding theories for correlated systems journal February 2017
Effect of propagator renormalization on the band gap of insulating solids journal August 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
To the Theory of Inhomogeneous Electron Gas journal August 2018
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
Ground state properties of 3d metals from self-consistent GW approach text January 2017
Spectral properties from Matsubara Green's function approach - application to molecules text January 2017
Effect of propagator renormalization on the band gap of insulating solids text January 2018
Legendre-spectral Dyson equation solver with super-exponential convergence text January 2020

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