Dynamical Kernels for Optical Excitations

Juliette Authier (1) , Pierre-Francois Loos (1)

1 GMO - Groupe THEO (LCPQ)

We discuss the physical properties and accuracy of three distinct dynamical (ie, frequency-dependent) kernels for the computation of optical excitations within linear response theory: i) an a priori built kernel inspired by the dressed time-dependent density-functional theory (TDDFT) kernel proposed by Maitra and coworkers, ii) the dynamical kernel stemming from the Bethe-Salpeter equation (BSE) formalism derived originally by Strinati , and iii) the second-order BSE kernel derived by Yang and coworkers . The principal take-home message of the present paper is that dynamical kernels can provide, thanks to their frequency-dependent nature, additional excitations that can be associated to higher-order excitations (such as the infamous double excitations), an unappreciated feature of dynamical quantities. We also analyze, for each kernel, the appearance of spurious excitations originating from the approximate nature of the kernels, as first evidenced by Romaniello. Using a simple two-level model, prototypical examples of valence, charge-transfer, and Rydberg excited states are considered.

Domaines: Chimie théorique et/ou physique

Juliette Authier, Pierre-Francois Loos. Dynamical Kernels for Optical Excitations. Journal of Chemical Physics, 2020, 153 (18), pp.184105. ⟨10.1063/5.0028040⟩. ⟨hal-02928388⟩