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Derivation and assessment of relativistic hyperfine-coupling tensors on the basis of orbital-optimized second-order Møller–Plesset perturbation theory and the second-order Douglas–Kroll–Hess transformation
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10.1063/1.4792362
/content/aip/journal/jcp/138/10/10.1063/1.4792362
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4792362

Figures

Image of FIG. 1.
FIG. 1.

The magnetization distribution for the hydrogen atom for the Gaussian nucleus model (black) as compared to the form-factor model (gray). At the maximum (r iN = 0), the Gaussian model is three orders of magnitude smaller than the form-factor model. Note that the y axis is logscale and units are atomic units.

Tables

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Table I.

In the first column, the hfc operators for nucleus N are given for the non-relativistic theory as they are derived from the Pauli Hamiltonian. The second and third columns show the respective contributions derived from the fpFW- and fπFW-based DKH-2 Hamiltonians. Boldface letters denote vectors and is the distance between electron i and nucleus N. As usual, Z N is the charge of the nucleus and g N μ N its magnetic moment. The fine-structure constant in SI-based atomic units used throughout this paper.

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Table II.

Listed are the hfc contributions for Cu and Cd in CdH, derived from the fpFW-based as well as from the fπFW-Hamiltonian. Calculations are carried out with a Gaussian, finite nucleus (fn), and point nucleus (pn) model. Values obtained for Cu result from a HF calculation, those for Cd from DFT with BP86.

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Table III.

The isotropic hfc for alkaline earth metal cations calculated with RI-MP2 and compared to the OO-RI-MP2 method, with and without second-order DKH picture-change effects. Four-component results and high-precision experiments serve as reference. All values are given in MHz.

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Table IV.

The isotropic hfc for group-12 atoms calculated with RI-MP2 and compared to the OO-RI-MP2 method, with and without second-order DKH picture-change effects. Four-component MCDF results and high-precision experiments serve as reference. All values are given in MHz.

Generic image for table
Table V.

The isotropic hfc for transition-metal complexes calculated with the OO-RI-MP2 method and second-order DKH corrections versus experimental results. Hfc values refer to the transition metal. A single value refers to the isotropic hfc, whereas for molecules with symmetry axis, the parallel and perpendicular components are listed (in that order). For all other complexes, x-, y- and z-eigenvalues of the hfc tensor are listed. For Mn(CO)5 and [Cu(en)2]2 +, is not included as the CP-SCF equations did not converge. All values are given in MHz.

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/content/aip/journal/jcp/138/10/10.1063/1.4792362
2013-03-08
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Derivation and assessment of relativistic hyperfine-coupling tensors on the basis of orbital-optimized second-order Møller–Plesset perturbation theory and the second-order Douglas–Kroll–Hess transformation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4792362
10.1063/1.4792362
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