Embedding beyond Electrostatics – The Role of Wave-Function Confinement


L. J. Nåbo, J. M. H. Olsen, N. H. List, L. M. Solanko, D. Wüstner, J. Kongsted

J. Chem. Phys. 2016, 145, 104102


We study excited states of cholesterol in solution and show that, in this specific case, solute wave-function confinement is the main effect of the solvent. This is rationalized on the basis of the polarizable density embedding scheme, which in addition to polarizable embedding includes non-electrostatic repulsion that effectively confines the solute wave function to its cavity. We illustrate how the inclusion of non-electrostatic repulsion results in a successful identification of the intense π → π transition, which was not possible using an embedding method that only includes electrostatics. This underlines the importance of non-electrostatic repulsion in quantum-mechanical embedding-based methods.