Embedding beyond electrostatics—The role of wave function confinement

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-electros...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-09, Vol.145 (10), p.104102-104102
Main Authors: Nåbo, Lina J., Olsen, Jógvan Magnus Haugaard, Holmgaard List, Nanna, Solanko, Lukasz M., Wüstner, Daniel, Kongsted, Jacob
Format: Article
Language:English
Subjects:
Cholesterol
Cholesterol - chemistry
Cholesterol - metabolism
Confinement
Electrostatics
Embedding
Ions
Molecular Conformation
Molecular Dynamics Simulation
Quantum Theory
Static Electricity
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Summary: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.
ISSN:0021-9606
1089-7690
1089-7690
DOI:10.1063/1.4962367