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
(Less)
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.
- author
- Hemmingsen, Lars
and Ryde, Ulf
LU
- organization
- publishing date
- 1996-03-21
- 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 (ACS)
- 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
- 2023-04-07 08:39:07
@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.</p>}},
author = {{Hemmingsen, Lars and Ryde, Ulf}},
issn = {{0022-3654}},
language = {{eng}},
month = {{03}},
number = {{12}},
pages = {{4803--4809}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of Physical Chemistry}},
title = {{Ab initio calculations of electric field gradients in cadmium complexes}},
url = {{http://dx.doi.org/10.1021/jp9526410}},
doi = {{10.1021/jp9526410}},
volume = {{100}},
year = {{1996}},
}