ic6b02312_si_002.cif (4.51 MB)
Magnetic Excitations in Polyoxotungstate-Supported Lanthanoid Single-Molecule Magnets: An Inelastic Neutron Scattering and ab Initio Study
dataset
posted on 2016-12-15, 16:18 authored by Michele Vonci, Marcus J. Giansiracusa, Willem Van den Heuvel, Robert W. Gable, Boujemaa Moubaraki, Keith S. Murray, Dehong Yu, Richard A. Mole, Alessandro Soncini, Colette BoskovicInelastic 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.