Polarizable Continuum Models and Green’s Function GW Formalism: On the Dynamics of the Solvent Electrons - Archive ouverte HAL
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2024

Polarizable Continuum Models and Green’s Function GW Formalism: On the Dynamics of the Solvent Electrons

Ivan Duchemin
David Amblard
Xavier Blase

Résumé

The many-body GW formalism, for the calculation of ionization potentials or electronic affinities, relies on the frequency-dependent dielectric function built from the electronic degrees of freedom. Considering the case of water as a solvent treated within the polarizable continuum model, we explore the impact of restricting the full frequency-dependence of the solvent electronic dielectric response to a frequency-independent (ϵ ∞ ) optical dielectric constant. For solutes presenting small to large highest-occupied to lowest-unoccupied molecular orbital energy gaps, we show that such a restriction induces errors no larger than a few percent on the energy level shifts from the gas to the solvated phase. We further introduce a remarkably accurate single-pole model for mimicking the effect of the full frequency dependence of the water dielectric function in the visible-UV range. This allows a fully dynamical embedded GW calculation with the only knowledge of the cavity reaction field calculated for the ϵ ∞ optical dielectric constant.

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hal-04752298 , version 1 (24-10-2024)

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Domaine public

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Ivan Duchemin, David Amblard, Xavier Blase. Polarizable Continuum Models and Green’s Function GW Formalism: On the Dynamics of the Solvent Electrons. Journal of Chemical Theory and Computation, 2024, 20 (20), pp.9072-9083. ⟨10.1021/acs.jctc.4c00745⟩. ⟨hal-04752298⟩
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