Employing Pseudopotentials to Tackle Excited-State Electron Spill-Out in Frozen Density Embedding Calculations.

Abstract

In frozen density embedding (FDE), the properties of a target molecule are computed in the presence of an effective embedding potential, which accounts for the attractive and repulsive contributions of the environment. The formally exact embedding potential, however, is in practice calculated using explicit kinetic-energy functionals for which the resulting potentials are in many cases not repulsive enough to account fully for Pauli repulsion by the electrons of the environment and to compensate thereby the strong electron-nuclear attraction. For the excited states on the target molecule, this leads to charge spill-out when diffuse basis functions are included, which allow that valence electrons are excited to those regions of the environment where the strong nuclear attraction is not sufficiently compensated by repulsive contributions. To reduce this insufficiency, we propose in the present work the inclusion of atomic all-electron pseudopotentials for all environment atoms on top of the conventional embedding potential. In the current work, the pseudopotentials are applied for computing vertical excitation energies of local excited states in complex systems employing the second-order algebraic diagrammatic construction (ADC(2)) scheme. The proposed approach leads to significantly reduced charge spill-out and an improved agreement of FDE and supermolecular calculations in the frozen solvent approximation. In particular, when diffuse functions are employed, the mean absolute deviation (MAD) is reduced from 0.27 to 0.05 eV for the investigated cases.