Accuracy of One- and Two-Photon Intensities with the Extended Polarizable Density Embedding Model.

Abstract

The recently developed extended polarizable density embedding (PDE-X) model is evaluated for the spectroscopic properties of organic chromophores solvated in water, including both one- and two-photon absorption properties. The PDE-X embedding model systematically improves vertical excitation energies over the preceding polarizable density embedding model (PDE). PDE-X shows more modest improvements over existing embedding models for oscillator strengths and two-photon absorption cross-sections, which are more sensitive properties. We argue that the origin of these discrepancies is related to the description of polarization effects, suggesting directions for future development of the embedding model.