Please use this identifier to cite or link to this item: https://doi.org/10.1002/chem.201501330
Title: Magnetic Relaxation in Single-Electron Single-Ion Cerium(III) Magnets: Insights from Ab Initio Calculations
Authors: Singh, Saurabh Kumar
Gupta, Tulika
Ungur, Liviu 
Rajaraman, Gopalan
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
cerium
density functional calculations
ligand effects
magnetic properties
MOLECULE-MAGNET
SMM BEHAVIOR
GROUND-STATE
COMPLEXES
ANISOTROPY
BLOCKING
DY
EXCHANGE
FAMILY
LIGAND
Issue Date: 21-Sep-2015
Publisher: WILEY-V C H VERLAG GMBH
Citation: Singh, Saurabh Kumar, Gupta, Tulika, Ungur, Liviu, Rajaraman, Gopalan (2015-09-21). Magnetic Relaxation in Single-Electron Single-Ion Cerium(III) Magnets: Insights from Ab Initio Calculations. CHEMISTRY-A EUROPEAN JOURNAL 21 (39) : 13812-13819. ScholarBank@NUS Repository. https://doi.org/10.1002/chem.201501330
Abstract: Detailed ab initio calculations were performed on two structurally different cerium(III) single-molecule magnets (SMMs) to probe the origin of magnetic anisotropy and to understand the mechanism of magnetic relaxations. The complexes [CeIII{ZnII(L)}2(MeOH)]BPh4 (1) and [Li(dme)3][CeIII(cot′′)2] (1; L=N,N,O,O-tetradentate Schiff base ligand; 2; DME=dimethoxyethane, COT′′=1,4-bis(trimethylsilyl)cyclooctatetraenyldianion), which are reported to be zero-field and field-induced SMMs with effective barrier heights of 21.2 and 30K respectively, were chosen as examples. CASSCF+RASSI/SINGLE-ANISO calculations unequivocally suggest that mJ|±5/2 and |±1/2 are the ground states for complexes 1 and 2, respectively. The origin of these differences is rooted back to the nature of the ligand field and the symmetry around the cerium(III) ions. Ab initio magnetisation blockade barriers constructed for complexes 1 and 2 expose a contrasting energy-level pattern with significant quantum tunnelling of magnetisation between the ground state Kramers doublet in complex 2. Calculations performed on several model complexes stress the need for a suitable ligand environment and high symmetry around the cerium(III) ions to obtain a large effective barrier. CeIII Jiggling! Some CeIII mononuclear complexes exhibit single-molecule magnetic (SMM) behaviour, whereas others do not (see figure). This intriguing point has been investigated by using ab initio calculations and the role of ligand field and symmetry in dictating SMM characteristics is highlighted.
Source Title: CHEMISTRY-A EUROPEAN JOURNAL
URI: https://scholarbank.nus.edu.sg/handle/10635/228722
ISSN: 0947-6539
1521-3765
DOI: 10.1002/chem.201501330
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