title: Magnetic Excitations in Polyoxotungstate-Supported Lanthanoid Single-Molecule Magnets: An Inelastic Neutron Scattering and ab Initio Study.
abstract: Inelastic neutron scattering (INS) has been used to investigate the crystal field (CF) magnetic excitations of the analogs of the most representative lanthanoid-polyoxometalate single-molecule magnet family: Na9[Ln(W5O18)2] (Ln = Nd, Tb, Ho, Er). Ab initio complete active space self-consistent field/restricted active space state interaction calculations, extended also to the Dy analog, show good agreement with the experimentally determined low-lying CF levels, with accuracy better in most cases than that reported for approaches based only on simultaneous fitting to CF models of magnetic or spectroscopic data for isostructural Ln families. In this work we demonstrate the power of a combined spectroscopic and computational approach. Inelastic neutron scattering has provided direct access to CF levels, which together with the magnetometry data, were employed to benchmark the ab initio results. The ab initio determined wave functions corresponding to the CF levels were in turn employed to assign the INS transitions allowed by selection rules and interpret the observed relative intensities of the INS peaks. Ultimately, we have been able to establish the relationship between the wave function composition of the CF split LnIIIground multiplets and the experimentally measured magnetic and spectroscopic properties for the various analogs of the Na9[Ln(W5O18)2] family.
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Michele
authors.identifier: http://orcid.org/0000-0002-0880-3225
authors.initials: M
authors.lastname: Vonci
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Marcus J
authors.initials: MJ
authors.lastname: Giansiracusa
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Willem
authors.identifier: http://orcid.org/0000-0003-4880-4449
authors.initials: W
authors.lastname: Van den Heuvel
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Robert W
authors.identifier: http://orcid.org/0000-0002-4626-0217
authors.initials: RW
authors.lastname: Gable
authors.affiliation: School of Chemistry, Monash University , Clayton, Victoria 3800, Australia.
authors.forename: Boujemaa
authors.initials: B
authors.lastname: Moubaraki
authors.affiliation: School of Chemistry, Monash University , Clayton, Victoria 3800, Australia.
authors.forename: Keith S
authors.initials: KS
authors.lastname: Murray
authors.affiliation: Australian Nuclear Science and Technology Organisation , Locked Bag 2001, Kirrawee DC, New South Wales 2232, Australia.
authors.forename: Dehong
authors.initials: D
authors.lastname: Yu
authors.affiliation: Australian Nuclear Science and Technology Organisation , Locked Bag 2001, Kirrawee DC, New South Wales 2232, Australia.
authors.forename: Richard A
authors.initials: RA
authors.lastname: Mole
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Soncini
authors.affiliation: School of Chemistry, University of Melbourne , Parkville, Victoria 3010, Australia.
authors.forename: Colette
authors.identifier: http://orcid.org/0000-0002-1882-2139
authors.initials: C
authors.lastname: Boskovic