TY - JOUR
T1 - Magnetic excitations in polyoxotungstate-supported lanthanoid single-molecule magnets
T2 - an inelastic neutron scattering and ab initio study
AU - Vonci, Michele
AU - Giansiracusa, Marcus J.
AU - Van Den Heuvel, Willem
AU - Gable, Robert W.
AU - Moubaraki, Boujemaa
AU - Murray, Keith
AU - Yu, Dehong
AU - Mole, Richard A.
AU - Soncini, Alessandro
AU - Boskovic, Colette
PY - 2017/1/3
Y1 - 2017/1/3
N2 - 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 LnIII ground multiplets and the experimentally measured magnetic and spectroscopic properties for the various analogs of the Na9[Ln(W5O18)2] family.
AB - 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 LnIII ground multiplets and the experimentally measured magnetic and spectroscopic properties for the various analogs of the Na9[Ln(W5O18)2] family.
UR - http://www.scopus.com/inward/record.url?scp=85008870038&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.6b02312
DO - 10.1021/acs.inorgchem.6b02312
M3 - Article
AN - SCOPUS:85008870038
SN - 0020-1669
VL - 56
SP - 378
EP - 394
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -