Berlin 2018 – wissenschaftliches Programm
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CPP: Fachverband Chemische Physik und Polymerphysik
CPP 55: Focus Session: Frontiers of Electronic-Structure Theory: Correlated Electron Materials V (joint session O/MM/DS/TT/CPP)
CPP 55.8: Vortrag
Mittwoch, 14. März 2018, 17:00–17:15, HL 001
A quantum embedding theory combining many-body perturbation theory with configuration interaction — •Marc Dvorak and Patrick Rinke — Department of Applied Physics, Aalto University School of Science, 00076-Aalto, Finland
We present a new quantum embedding theory called dynamical configuration interaction (DCI). It captures non-local and static correlation in an orbital active space with configuration interaction (CI) and high-energy, dynamic correlation in the complementary bath space with many-body perturbation theory (MBPT). The formulation is general, but we focus on molecular systems with an ab-initio Hamiltonian. The conceptual key to our approach is to replace the exact electronic Hamiltonian in the bath space with one of excitations defined over the correlated ground state. This transformation is naturally suited to the language and methodology of many-body Green’s functions. Correlation in the bath is therefore described at the quasiparticle level with Green’s functions instead of with the many-body wave function. Our approach avoids computational and conceptual difficulties associated with Green’s function embedding and improves upon wave function methods by including dynamical correlation from the bath space. A major advantage to DCI is that it naturally treats ground and excited states on equal quantum mechanical levels. For ground state properties, we present dimer dissociation curves for H2 and N2 in excellent agreement with exact results. Excited states of N2 give excellent agreement with experiment, and we demonstrate the scalability of our method by computing excited states of a free-base porphyrin molecule.