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Theoretical Studies on Polynuclear {(Cu5GdnIII)-Gd-II} Clusters (n=4, 2): Towards Understanding Their Large Magnetocaloric Effect

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Title Theoretical Studies on Polynuclear {(Cu5GdnIII)-Gd-II} Clusters (n=4, 2): Towards Understanding Their Large Magnetocaloric Effect
 
Creator RAJESHKUMAR, T
ANNADATA, HV
EVANGELISTI, M
LANGLEY, SK
CHILTON, NF
MURRAY, KS
RAJARAMAN, G
 
Subject TRANSITION-METAL CLUSTERS
MAGNETIC-PROPERTIES
MOLECULAR MAGNETS
GROUND-STATE
EXCHANGE INTERACTIONS
COPPER(II) COMPLEXES
BINUCLEAR COMPLEXES
III COMPLEXES
CR-III
HYDROXO
 
Description Density functional theory (DFT) studies on two polynuclear clusters, [(Cu5Gd4O2)-Gd-II-O-III(OMe)(4)(teaH)(4)(O2CC(CH3)(3))(2)(NO3)(4)] (1) and [Cu5Gd2(OH)(4)(Br)(2)-(H2L)(2)(H3L)(2)(NO3)(2)(OH2)(4)] (2), have been carried out to probe the origin of the large magnetocaloric effect (MCE). The magnetic exchange interactions for 1 and 2 via multiple pathways are estimated using DFT calculations. While the calculated exchange parameters deviate from previous experimental estimates obtained by fitting the magnetic data, the DFT parameter set is found to offer a striking match to the magnetic data for both complexes, highlighting the problem of overparameterization. Magnetostructural correlations for {Cu-Gd} pairs have been developed where both the Cu-O-Gd angles and Cu-O-Gd-O dihedral angles are found to significantly influence the magnitude and sign of the exchange constants. The magnitude of the MCE has been examined as a function of the exchange interactions, and clues on how the effect can be enhanced are discussed.
 
Publisher AMER CHEMICAL SOC
 
Date 2016-01-15T06:24:05Z
2016-01-15T06:24:05Z
2015
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 54(4)1661-1670
0020-1669
1520-510X
http://dx.doi.org/10.1021/ic502651w
http://dspace.library.iitb.ac.in/jspui/handle/100/17924
 
Language en