Improved One-Shot Total Energies from the Linearized GW Density Matrix

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Journal of Chemical Theory and Computation
The linearized GW density matrix (γGW) is an efficient method to improve the static portion of the self-energy compared to that of ordinary perturbative GW while keeping the single-shot simplicity of the calculation. Previous work has shown that γGW gives an improved Fock operator and total energy components that approach the self-consistent GW quality. Here, we test γGW for dimer dissociation for the first time by studying N2, LiH, and Be2. We also calculate a set of self-consistent GW results in identical basis sets for a direct and consistent comparison. γGW approaches self-consistent GW total energies for a starting point based on a high amount of exact exchange. We also compare the accuracy of different total energy functionals, which differ when evaluated with a non-self-consistent density or density matrix. While the errors in total energies among different functionals and starting points are small, the individual energy components show noticeable errors when compared to reference data. The energy component errors of γGW are smaller than functionals of the density and we suggest that the linearized GW density matrix is a route to improving total energy evaluations in the adiabatic connection framework.
Funding Information: F.B. and M.R.M. acknowledge the financial support of the Cross-Disciplinary Program on Numerical Simulation of CEA, the French Alternative Energies and Atomic Energy Commission. This work was performed using HPC resources from GENCI-TGCC and GENCI-IDRIS (grant 2020-gen6018). M.D. was supported by the Academy of Finland through a postdoctoral grant no. 316347 and acknowledges the CSC—IT Center for Science, Finland, and the Aalto Science-IT project for computational resources. a Publisher Copyright: © 2020 American Chemical Society. All rights reserved. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
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Bruneval , F , Rodriguez-Mayorga , M , Rinke , P & Dvorak , M 2021 , ' Improved One-Shot Total Energies from the Linearized GW Density Matrix ' , Journal of Chemical Theory and Computation , vol. 17 , no. 4 , pp. 2126-2136 .