The Source Function (SF) tool was applied to the analysis of the theoretical spin density in azido CuII dinuclear complexes, where the azido group, acting as a coupler between the CuII cations, is linked to the metal centres either in an end-on or in an end-end fashion. Results for only the former structural arrangement are reported in the present paper. The SF highlights to which extent the magnetic centres contribute to determine the local spin delocalization and polarization at any point in the dimetallic complex and whether an atom or group of atoms of the ligands act in favour or against a given local spin delocalization/polarization. Ball-and-stick atomic SF percentage representations allow for a visualization of the magnetic pathways and of the specific role played by each atom along these paths, at given reference points. Decomposition of SF contributions in terms of a magnetic and of a relaxation component provides further insight. Reconstruction of partial spin densities by means of the Source Function has for the first time been introduced. At variance with the standard SF percentage representations, such reconstructions offer a simultaneous view of the sources originating from specific subsets of contributing atoms, in a selected molecular plane or in the whole space, and are therefore particularly informative. The SF tool is also used to evaluate the accuracy of the analysed spin densities. It is found that those obtained at the unrestricted B3LYP DFT level, relative to those computed at the CASSCF(6,6) level, greatly overestimate spin delocalization to the ligands, but comparatively underestimate magnetic connection (spin transmission) among atoms, along the magnetic pathways. As a consequence of its excessive spin delocalization, the UB3LYP method also overestimates spin polarization mechanisms between the paramagnetic centres and the ligands. Spin delocalization measures derived from the refinement of Polarized Neutron Diffraction data seem in general superior to those obtained through the DFT UB3LYP approach and closer to the far more accurate CASSCF results. It is also shown that a visual agreement on the spin-resolved electron densities rho(alpha) and rho(beta) derived from different approaches does not warrant a corresponding agreement between their associated spin densities.Electron spin density at a point may be seen as determined by a local Source Function for such density, operating at all other points of space. Integration of the local source over Bader's quantum atoms measures their contribution in determining the spin density features at any system's location. This novel tool is able to provide interesting insights on the electron spin delocalization and polarization mechanisms along with their dependence from the spin density quality.

Insights on spin delocalization and spin polarization mechanisms in crystals of azido copper(II) dinuclear complexes through the electron spin density Source Function / C. Gatti, G. Macetti, L. Lo Presti. - In: ACTA CRYSTALLOGRAPHICA. SECTION B, STRUCTURAL SCIENCE, CRYSTAL ENGINEERING AND MATERIALS. - ISSN 2052-5192. - 73:4(2017 Aug 01), pp. 565-583. [10.1107/S2052520617008083]

Insights on spin delocalization and spin polarization mechanisms in crystals of azido copper(II) dinuclear complexes through the electron spin density Source Function

G. Macetti;L. Lo Presti
2017-08-01

Abstract

The Source Function (SF) tool was applied to the analysis of the theoretical spin density in azido CuII dinuclear complexes, where the azido group, acting as a coupler between the CuII cations, is linked to the metal centres either in an end-on or in an end-end fashion. Results for only the former structural arrangement are reported in the present paper. The SF highlights to which extent the magnetic centres contribute to determine the local spin delocalization and polarization at any point in the dimetallic complex and whether an atom or group of atoms of the ligands act in favour or against a given local spin delocalization/polarization. Ball-and-stick atomic SF percentage representations allow for a visualization of the magnetic pathways and of the specific role played by each atom along these paths, at given reference points. Decomposition of SF contributions in terms of a magnetic and of a relaxation component provides further insight. Reconstruction of partial spin densities by means of the Source Function has for the first time been introduced. At variance with the standard SF percentage representations, such reconstructions offer a simultaneous view of the sources originating from specific subsets of contributing atoms, in a selected molecular plane or in the whole space, and are therefore particularly informative. The SF tool is also used to evaluate the accuracy of the analysed spin densities. It is found that those obtained at the unrestricted B3LYP DFT level, relative to those computed at the CASSCF(6,6) level, greatly overestimate spin delocalization to the ligands, but comparatively underestimate magnetic connection (spin transmission) among atoms, along the magnetic pathways. As a consequence of its excessive spin delocalization, the UB3LYP method also overestimates spin polarization mechanisms between the paramagnetic centres and the ligands. Spin delocalization measures derived from the refinement of Polarized Neutron Diffraction data seem in general superior to those obtained through the DFT UB3LYP approach and closer to the far more accurate CASSCF results. It is also shown that a visual agreement on the spin-resolved electron densities rho(alpha) and rho(beta) derived from different approaches does not warrant a corresponding agreement between their associated spin densities.Electron spin density at a point may be seen as determined by a local Source Function for such density, operating at all other points of space. Integration of the local source over Bader's quantum atoms measures their contribution in determining the spin density features at any system's location. This novel tool is able to provide interesting insights on the electron spin delocalization and polarization mechanisms along with their dependence from the spin density quality.
polarized neutron diffraction; Source Function; spin delocalization; spin density; spin density quality; spin information transmission; spin polarization; Electronic, Optical and Magnetic Materials; Atomic and Molecular Physics, and Optics; 2506; Materials Chemistry; Metals and Alloys
Settore CHIM/02 - Chimica Fisica
Settore CHIM/03 - Chimica Generale e Inorganica
ACTA CRYSTALLOGRAPHICA. SECTION B, STRUCTURAL SCIENCE, CRYSTAL ENGINEERING AND MATERIALS
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/522034
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