title: Embedding beyond electrostatics-The role of wave function confinement.
abstract: 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.
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
authors.forename: Lina J
authors.initials: LJ
authors.lastname: Nåbo
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
authors.forename: Jógvan Magnus Haugaard
authors.initials: JM
authors.lastname: Olsen
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, SE-106 91 Stockholm, Sweden.
authors.forename: Nanna
authors.initials: N
authors.lastname: Holmgaard List
authors.affiliation: Orphazyme ApS, Ole Maaløes Vej 3, 2200 Copenhagen N, Denmark.
authors.forename: Lukasz M
authors.initials: LM
authors.lastname: Solanko
authors.affiliation: Department of Biochemistry and Molecular Biology, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
authors.forename: Daniel
authors.initials: D
authors.lastname: Wüstner
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
authors.forename: Jacob
authors.initials: J
authors.lastname: Kongsted
mesh_terms: D002784:Cholesterol / Q000737:chemistry* / Q000378:metabolism; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D055672:Static Electricity
chemical_list: D002784:Cholesterol