Combining wavefunction frozen-density embedding with one-dimensional periodicity

Abstract

We present the combination of wavefunction frozen-density embedding (FDE) with a periodic repetition in one dimension (1D) for molecular systems in the KOALA program. In this periodic orbital-uncoupled FDE ansatz, no wavefunction overlap is taken into account, and only the electron density of the active subsystem is computed explicitly. This density is relaxed in the presence of the environment potential, which is obtained by translating the updated active subsystem density, yielding a fully self-consistent solution at convergence. Treating only one subsystem explicitly, the method allows for the calculation of local properties in condensed molecular systems, while no orbital band structure is obtained preventing the application, e.g., to systems with metallic bonding. In order to illustrate possible applications of the new implementation, selected case studies are presented, ranging from ground-state dipole moments using configuration interaction methods via excitation energies using time-dependent density-functional theory to ionization potentials obtained from equation-of-motion correlation methods. Different levels of approximations are assessed, revealing that an active subsystem consisting of two or three molecules leads to results that are converged with respect to the environment contributions.