Optical determination of the single-ion zero-field splitting in large spin clusters

David Collison; Vasily S Oganesyan; Stergios Piligkos; Andrew J Thomson; Richard E P Winpenny; Eric J L McInnes

doi:10.1021/ja029003x

Optical determination of the single-ion zero-field splitting in large spin clusters

J Am Chem Soc. 2003 Feb 5;125(5):1168-9. doi: 10.1021/ja029003x.

Authors

David Collison¹, Vasily S Oganesyan, Stergios Piligkos, Andrew J Thomson, Richard E P Winpenny, Eric J L McInnes

Affiliation

¹ Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.

PMID: 12553809
DOI: 10.1021/ja029003x

Abstract

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.