Optical determination of the single-ion zero-field splitting in large spin clusters.
The dodecametallic Cr(III) cluster has an S = 6 ground state with an axial zero-field splitting (ZFS) of DS=6 = +0.088 cm-1. Analysis of high-resolution optical data (MCD) allows us to determine the single-ion ZFS of the constituent Cr(III) ions directly (D = -1.035 cm-1). A vector coupling analysis demonstrates that the cluster ZFS is almost entirely single-ion in origin. Thus, the relative orientations of the local and cluster magnetic axes can lead to cluster ZFS of opposite sign to the single-ion even when this is the only significant contribution.
Collison
David
D
Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Oganesyan
Vasily S
VS
Piligkos
Stergios
S
Thomson
Andrew J
AJ
Winpenny
Richard E P
RE
McInnes
Eric J L
EJ