Embedding beyond electrostatics: The role of wave function confinement

Lina J. Nåbo, Jógvan Magnus Haugaard Olsen, Nanna Holmgaard List, Lukasz M. Solanko, Daniel Wüstner, Jacob Kongsted

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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.

Original languageEnglish
Article number104102
JournalThe Journal of Chemical Physics
Volume145
Number of pages7
ISSN0021-9606
DOIs
Publication statusPublished - 14. Sep 2016

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Wave functions
embedding
Electrostatics
wave functions
electrostatics
Excited states
solutes
Cholesterol
cholesterol
inclusions
cavities
excitation

Cite this

Nåbo, Lina J. ; Olsen, Jógvan Magnus Haugaard ; Holmgaard List, Nanna ; Solanko, Lukasz M. ; Wüstner, Daniel ; Kongsted, Jacob. / Embedding beyond electrostatics : The role of wave function confinement. In: The Journal of Chemical Physics. 2016 ; Vol. 145.
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Embedding beyond electrostatics : The role of wave function confinement. / Nåbo, Lina J.; Olsen, Jógvan Magnus Haugaard; Holmgaard List, Nanna; Solanko, Lukasz M.; Wüstner, Daniel; Kongsted, Jacob.

In: The Journal of Chemical Physics, Vol. 145, 104102, 14.09.2016.

Research output: Contribution to journalJournal articleResearchpeer-review

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