Embedding beyond electrostatics-The role of wave function confinement
2016 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 145, no 10, 104102Article in journal (Refereed) Published
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 pi ->pi* 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.
Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2016. Vol. 145, no 10, 104102
IdentifiersURN: urn:nbn:se:kth:diva-194271DOI: 10.1063/1.4962367ISI: 000383959000004ScopusID: 2-s2.0-84987761900OAI: oai:DiVA.org:kth-194271DiVA: diva2:1039921
QC 201610252016-10-252016-10-212016-10-25Bibliographically approved