Direct observation of singlet-triplet separation in dimeric copper(II) acetate by neutron inelastic scattering spectroscopy

Guedel, Hans U.; Stebler, A.; Fürrer, A.

doi:10.1021/ic50194a029

Cited by 80 publications

(42 citation statements)

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“…Bleaney and Bowers first recognized the triplet state epr spectrum of copper(I1) acetate monohydrate (4) and solved the S = 1 spin Hamiltonian parameters. 'There is strong antiferromagnetic coupling in such dimers and a -25 value of 298 + 4 cm-' was determined recently by direct spectroscopic measurements by neutron scattering (5).…”

Section: Introductionmentioning

confidence: 82%

Copper(II) acetates: from dimer to monomer

Sharrock¹,

Melnı́k²

1985

Can. J. Chem.

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PATRICK SHARROCK and MILAN MELNIK. Can. J. Chem. 63, 52 (1985). The epr spectra at various frequencies of copper(l1) acetate anhydrous, monohydrate, monoacetic acid, and water -acetic acid adduct are presented and analysed. The presence of copper hyperfine splittings in the solid state epr spectra of this series of compounds is discussed. The frozen solution spectrum of copper(l1) acetate in acetic acid solution containing -2% water shows an exceptional resolution of A , hyperfine of 24 G. This is attributed to a key intermediate which explains the monomer-dimer dissociation mechanism. The influence of distortions on the structures of these compounds is presented.

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Section: Introductionmentioning

confidence: 82%

Copper(II) acetates: from dimer to monomer

Sharrock¹,

Melnı́k²

1985

Can. J. Chem.

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“…[3,92,93] It is extremely important to use a good crystal structure determination in order to reproduce the coupling constant properly, since deviations in the geometrical parameters can induce large changes in the calculated coupling constant. For instance, we have calculated the coupling constant of copper acetate using the geometry taken from an earlier structural determination.…”

Section: Computational Methodologymentioning

confidence: 99%

Exchange Coupling in Carboxylato-Bridged Dinuclear Copper(II) Compounds: A Density Functional Study

et al. 2001

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A computational study of the exchange coupling is presented for a selected sample of carboxylato-bridged dinuclear copper(II) compounds. Model calculations have been used to examine the influence of several factors on the coupling constants: a) the electron-withdrawing power of the bridging ligands; b) the nature of the axial ligands; c) the number of bridging carboxylato groups; d) some structural distortions frequently found in this family of compounds; and e) the coordination mode of the carboxylato bridge. Coupling constants calculated for some complete structures, as determined by X-ray diffraction, are in excellent agreement with experimental data, confirming the ability of the computational strategy used in this work to predict the coupling constant for compounds for which experimental data are not yet available.

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“…The nature of the magnetic interaction in this system was a matter of controversy during three decades: Do the two d x 2 -y 2 unpaired electrons interact directly via a ␦-bond or indirectly through the acetato-ligands? 37 The experimental works of Güdel et al 38 ͑around Ϫ1000 cm Ϫ1 ͒, well established from Raman 40 and neutron diffraction 41 experiments. Different theoretical approaches have been employed to evaluate J ͓for instance, finite 8 and periodic 42 DFT calculations, nonorthogonal CI ͑Ref.…”

Section: Description Of the Models And Computational Detailsmentioning

confidence: 98%

Analysis of the magnetic coupling in binuclear complexes. I. Physics of the coupling

Calzado

Cabrero

Malrieu

et al. 2002

The Journal of Chemical Physics

289

233

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Accurate estimates of the magnetic coupling in binuclear complexes can be obtained from ab initio configuration interaction ͑CI͒ calculations using the difference dedicated CI technique. The present paper shows that the same technique also provides a way to analyze the various physical contributions to the coupling and performs numerical analysis of their respective roles on four binuclear complexes of Cu (d 9 ) ions. The bare valence-only description ͑including direct and kinetic exchange͒ does not result in meaningful values. The spin-polarization phenomenon cannot be neglected, its sign and amplitude depend on the system. The two leading dynamical correlation effects have an antiferromagnetic character. The first one goes through the dynamical polarization of the environment in the ionic valence bond forms ͑i.e., the M ϩ¯MϪ structures͒. The second one is due to the double excitations involving simultaneously single excitations between the bridging ligand and the magnetic orbitals and single excitations of the environment. This dispersive effect results in an increase of the effective hopping integral between the magnetic orbitals. Moreover, it is demonstrated to be responsible for the previously observed larger metal-ligand delocalization occurring in natural orbitals with respect to the Hartree-Fock ones.

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Direct observation of singlet-triplet separation in dimeric copper(II) acetate by neutron inelastic scattering spectroscopy

Cited by 80 publications

References 0 publications

Copper(II) acetates: from dimer to monomer

Copper(II) acetates: from dimer to monomer

Exchange Coupling in Carboxylato-Bridged Dinuclear Copper(II) Compounds: A Density Functional Study

Analysis of the magnetic coupling in binuclear complexes. I. Physics of the coupling

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