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Journal of Chemical Physics / Volume 110 / Issue 16 / THEORETICAL METHODS AND ALGORITHMS

J. Chem. Phys. 110, 7689 (1999); http://dx.doi.org/10.1063/1.478680 (10 pages)

Density functional calculations of nuclear magnetic shieldings using the zeroth-order regular approximation (ZORA) for relativistic effects: ZORA nuclear magnetic resonance

S. K. Wolff1, T. Ziegler1, E. van Lenthe2, and E. J. Baerends2

1Department of Chemistry, The University of Calgary, Calgary, Alberta, T2N 1N4, Canada
2Afdeling Theoretisch Chemie, Scheikundig Laboratorium der Vrije Universiteit De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands

(Received 20 October 1998; accepted 29 December 1998)

We present a new relativistic formulation for the calculation of nuclear magnetic resonance (NMR) shielding tensors. The formulation makes use of gauge-including atomic orbitals and is based on density functional theory. The relativistic effects are included by making use of the zeroth-order regular approximation. This formulation has been implemented and the 199Hg NMR shifts of HgMe2, HgMeCN, Hg(CN)2, HgMeCl, HgMeBr, HgMeI, HgCl2, HgBr2, and HgI2 have been calculated using both experimental and optimized geometries. For experimental geometries, good qualitative agreement with experiment is obtained. Quantitatively, the calculated results deviate from experiment on average by 163 ppm, which is approximately 3% of the range of 199Hg NMR. The experimental effects of an electron donating solvent on the mercury shifts have been reproduced with calculations on HgCl2(NH3)2, HgBr2(NH3)2, and HgI2(NH3)2. In addition, it is shown that the mercury NMR shieldings are sensitive to geometry with changes for HgCl2 of approximately 50 ppm for each 0.01 Å  change in bond length, and 100 ppm for each 10° change in bond angle. © 1999 American Institute of Physics.

© 1999 American Institute of Physics

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KEYWORDS and PACS

Keywords

mercury compounds, nuclear magnetic resonance, density functional theory, nuclear screening, relativistic corrections, tensors, orbital calculations, organic compounds

PACS

  • 33.25.+k

    Nuclear resonance and relaxation

  • 31.30.J-

    Relativistic and quantum electrodynamic (QED) effects in atoms, molecules, and ions

  • 31.15.E-

    Density-functional theory

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.478680

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
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    E. van Lenthe, E. J. Baerends, and J. G. Snijders, J. Chem. Phys. 101, 9783 (1994)JCPSA6000101000011009783000001.

    A. J. Sadlej, J. G. Snijders, E. van Lenthe, and E. J. Baerends, J. Chem. Phys. 102, 1758 (1995)JCPSA6000102000004001758000001.

    S. K. Wolff and T. Ziegler, J. Chem. Phys. 109, 895 (1998)JCPSA6000109000003000895000001.

    E. van Lenthe, P. E. S. Wormer, and A. van der Avoird, J. Chem. Phys. 107, 2488 (1997)JCPSA6000107000007002488000001.

    J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).

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