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Issue 47, 2011
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Relativistic effects on group-12 metal nuclear shieldings

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Abstract

The leading-order perturbation theory approach to relativistic effects on the nuclear magnetic shielding provides an economic method for obtaining the chemical shifts in heavy-element containing systems. The method features detailed analysis potential in terms of the different physical mechanisms affecting the shielding tensors of heavy nuclei. The perturbative nature, however, results in an increasing error with increasingly heavy elements in the system. In this work, we investigate the performance of the Breit–Pauli perturbation theory (BPPT) against fully relativistic four-component theory in computing the nuclear shielding constants as well as the chemical shifts with respect to corresponding atomic ions of group-12 metals, M = Zn, Cd, and Hg, in dimethyl M(CH3)2 and aqueous M(H2O)62+ complexes. It is shown that five out of the total of sixteen BPPT correction terms are responsible for most of the relativistic corrections for the chemical shift of studied metals. The relativity is important already for Cd and BPPT is proven to work well up to Hg for the chemical shift, as calibrated with the fully relativistic method.

Graphical abstract: Relativistic effects on group-12 metal nuclear shieldings

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Publication details

The article was received on 22 Jun 2011, accepted on 29 Sep 2011 and first published on 20 Oct 2011


Article type: Paper
DOI: 10.1039/C1CP22043H
Citation: Phys. Chem. Chem. Phys., 2011,13, 21016-21025
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    Relativistic effects on group-12 metal nuclear shieldings

    J. Roukala, A. F. Maldonado, J. Vaara, G. A. Aucar and P. Lantto, Phys. Chem. Chem. Phys., 2011, 13, 21016
    DOI: 10.1039/C1CP22043H

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