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dc.contributor.authorList, Nanna Holmgaard
dc.contributor.authorBeerepoot, Maarten T. P.
dc.contributor.authorOlsen, Jógvan Magnus Haugaard
dc.contributor.authorGao, Bin
dc.contributor.authorRuud, Kenneth
dc.contributor.authorJensen, Hans Jørgen Aagaard
dc.contributor.authorKongsted, Jacob
dc.date.accessioned2016-02-23T09:14:39Z
dc.date.available2016-02-23T09:14:39Z
dc.date.issued2015-01-21
dc.description.abstractWe present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C==O group of acetophenone in different solvents and derive its vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization between acetophenone and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger extent on the quality of the Lennard-Jones parameters.en_US
dc.descriptionPublished version available at <a href=http://dx.doi.org/10.1063/1.4905909>http://dx.doi.org/10.1063/1.4905909</a>en_US
dc.identifier.citationJournal of Chemical Physics 2015, 142(3):034119en_US
dc.identifier.cristinIDFRIDAID 1257755
dc.identifier.doi10.1063/1.4905909
dc.identifier.issn1089-7690
dc.identifier.urihttps://hdl.handle.net/10037/8533
dc.identifier.urnURN:NBN:no-uit_munin_8102
dc.language.isoengen_US
dc.publisherAmerican Institute of Physics (AIP)en_US
dc.relation.projectIDEU: 279619en_US
dc.relation.projectIDNotur/NorStore: NN4654Ken_US
dc.relation.projectIDNorges forskningsråd: 179568en_US
dc.rights.accessRightsopenAccess
dc.subjectVDP::Matematikk og Naturvitenskap: 400en_US
dc.subjectVDP::Mathematics and natural science: 400en_US
dc.titleMolecular quantum mechanical gradients within the polarizable embedding approach-Application to the internal vibrational Stark shift of acetophenoneen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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