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arXiv · 2212.08982

Exact relationships between the GW approximation and equation-of-motion coupled-cluster theories through the quasi-boson formalism

Johannes Tölle·Garnet Kin-Lic Chan
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Abstract

We describe the relationship between the GW approximation and various equation-of-motion (EOM) coupled-cluster (CC) theories. We demonstrate the exact equivalence of the G$_0$W$_0$ approximation and the propagator theory for an electron-boson problem in a particular excitation basis. From there, we establish equivalence within the quasi-boson picture to the IP+EA-EOM unitary coupled-cluster propagator. We analyze the incomplete description of screening provided by the standard similarity-transformed IP+EA-EOM-CC and the recently introduced G$_0$W$_0$ Tamm-Dancoff approximation. We further consider the approximate decoupling of IP and EA sectors in EOM-CC treatments and devise the analogous particle-hole decoupling approach for the G$_0$W$_0$ approximation. Finally, we numerically demonstrate the exact relationships and magnitude of the approximations in calculations of a set of molecular ionization potentials and electron affinities.

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Johannes Tölle, Garnet Kin-Lic Chan. 2022-12-18. Exact relationships between the GW approximation and equation-of-motion coupled-cluster theories through the quasi-boson formalism. https://doi.org/10.1063/5.0139716

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