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Ab initio calculations of electric field gradients in cadmium complexes

Hemmingsen, Lars and Ryde, Ulf LU (1996) In Journal of Physical Chemistry 100(12). p.4803-4809
Abstract

Calculations of the electric field gradient (EFG) at the cadmium nucleus have been carried out on Cd2+ in the field of two point charges, CdF2, CdCl2, and CdF2Cl2
2- at the RHF, MPn (n = 2, 3, 4), and CCSD(T) levels of theory, in order to evaluate the effects of electron correlation, relativity, and basis set truncation. The EFG has furthermore been calculated in two large molecules (approximately 300 electrons) with biologically relevant cadmium ligands. Different methods to truncate the system have been investigated. The results are compared to experimental values determined in polycrystalline samples. We suggest a reasonably accurate and economic procedure to... (More)

Calculations of the electric field gradient (EFG) at the cadmium nucleus have been carried out on Cd2+ in the field of two point charges, CdF2, CdCl2, and CdF2Cl2
2- at the RHF, MPn (n = 2, 3, 4), and CCSD(T) levels of theory, in order to evaluate the effects of electron correlation, relativity, and basis set truncation. The EFG has furthermore been calculated in two large molecules (approximately 300 electrons) with biologically relevant cadmium ligands. Different methods to truncate the system have been investigated. The results are compared to experimental values determined in polycrystalline samples. We suggest a reasonably accurate and economic procedure to calculate the EFG on large cadmium complexes. The basis set on cadmium should be large, at least [19s15p9d4f/11s9p5d2f], while 6-31G(d) can be used on the remaining atoms. Correlation should be treated at least at the MP2 level, which is found to be unexpectedly accurate due to cancellation of higher order terms. In this treatment the core orbitals on the ligands and 1s through 3d orbitals on cadmium can be frozen. Surrounding molecules in the crystals have been modeled by an array of point charges. Using this procedure, the error of the elements of the diagonalized EFG tensor is less than 0.3 au (3 × 1021 V/m2) for the investigated complexes. © 1996 American Chemical Society.

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author
organization
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type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry
volume
100
issue
12
pages
7 pages
publisher
The American Chemical Society
external identifiers
  • scopus:0000112383
ISSN
0022-3654
DOI
10.1021/jp9526410
language
English
LU publication?
yes
id
febfaa2b-15a7-4a20-92db-ff082e3307e4
date added to LUP
2017-02-04 11:33:45
date last changed
2017-07-02 04:58:57
@article{febfaa2b-15a7-4a20-92db-ff082e3307e4,
  abstract     = {<p>Calculations of the electric field gradient (EFG) at the cadmium nucleus have been carried out on Cd<sup>2+</sup> in the field of two point charges, CdF<sub>2</sub>, CdCl<sub>2</sub>, and CdF<sub>2</sub>Cl<sub>2</sub><br>
<sup>2-</sup> at the RHF, MPn (n = 2, 3, 4), and CCSD(T) levels of theory, in order to evaluate the effects of electron correlation, relativity, and basis set truncation. The EFG has furthermore been calculated in two large molecules (approximately 300 electrons) with biologically relevant cadmium ligands. Different methods to truncate the system have been investigated. The results are compared to experimental values determined in polycrystalline samples. We suggest a reasonably accurate and economic procedure to calculate the EFG on large cadmium complexes. The basis set on cadmium should be large, at least [19s15p9d4f/11s9p5d2f], while 6-31G(d) can be used on the remaining atoms. Correlation should be treated at least at the MP2 level, which is found to be unexpectedly accurate due to cancellation of higher order terms. In this treatment the core orbitals on the ligands and 1s through 3d orbitals on cadmium can be frozen. Surrounding molecules in the crystals have been modeled by an array of point charges. Using this procedure, the error of the elements of the diagonalized EFG tensor is less than 0.3 au (3 × 10<sup>21</sup> V/m<sup>2</sup>) for the investigated complexes. © 1996 American Chemical Society.</p>},
  author       = {Hemmingsen, Lars and Ryde, Ulf},
  issn         = {0022-3654},
  language     = {eng},
  month        = {03},
  number       = {12},
  pages        = {4803--4809},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry},
  title        = {Ab initio calculations of electric field gradients in cadmium complexes},
  url          = {http://dx.doi.org/10.1021/jp9526410},
  volume       = {100},
  year         = {1996},
}