The self-consistent-field multiple-scattering Xa method has been used to calculate the electronic structure of pseudotetrahedral and square-planar CuCI4*- ions, with the aim of checking the reliability of the method in the calculation of the spectral (electronic and EPR) properties of transition metal complexes. Several different calculation schemes were used in order to improve the fit to the experimental spectral transitions. Overlapping spheres were found to give the best agreement. The values of g and of the 63Cu hyperfine constant were satisfactorily reproduced, showing that the low value of the latter in the pseudotetrahedral ion is due to covalency effects and not to 4p metal orbital mixing into the ground state.

X.alpha. calculations of the EPR parameters of pseudotetrahedral copper(II) complexes / Alessandro Bencini;Dante Gatteschi. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 105:(1983), pp. 5535-5541. [10.1021/ja00355a002]

X.alpha. calculations of the EPR parameters of pseudotetrahedral copper(II) complexes

BENCINI, ALESSANDRO;GATTESCHI, DANTE
1983

Abstract

The self-consistent-field multiple-scattering Xa method has been used to calculate the electronic structure of pseudotetrahedral and square-planar CuCI4*- ions, with the aim of checking the reliability of the method in the calculation of the spectral (electronic and EPR) properties of transition metal complexes. Several different calculation schemes were used in order to improve the fit to the experimental spectral transitions. Overlapping spheres were found to give the best agreement. The values of g and of the 63Cu hyperfine constant were satisfactorily reproduced, showing that the low value of the latter in the pseudotetrahedral ion is due to covalency effects and not to 4p metal orbital mixing into the ground state.
1983
105
5535
5541
Alessandro Bencini;Dante Gatteschi
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/654930
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