A formulation and implementation of the quadratic response function in the adiabatic four-component Kohn-Sham approximation is presented. The noninteracting reference state is time-reversal symmetric and formed from Kramers pair spinors, and the energy density is gradient corrected. Example calculations are presented for the optical properties of disubstituted halobenzenes in their meta and ortho conformations. It is demonstrated that correlation and relativistic effects are not additive, and it is shown that relativity alone reduces the -response signal by 62% and 75% for meta- and ortho-bromobenzene, respectively, and enhances the same response by 17% and 21% for meta- and ortho-iodobenzene, respectively. Of the employed functionals, CAM-B3LYP shows the best performance and gives hyperpolarizabilities distinctly different from B3LYP.
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14 January 2008
Research Article|
January 10 2008
Quadratic response functions in the relativistic four-component Kohn-Sham approximation
Johan Henriksson;
Johan Henriksson
Department of Physics, Chemistry and Biology,
Linköping University
, SE-581 83 Linköping, Sweden
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Trond Saue;
Trond Saue
Institut de Chimie,
UMR 7177 CNRS et Université Louis Pasteur
, 4 rue Blaise Pascal, F-67000 Strasbourg, France
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Patrick Norman
Patrick Norman
a)
Department of Physics, Chemistry and Biology,
Linköping University
, SE-581 83 Linköping, Sweden
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a)
Electronic mail: [email protected].
J. Chem. Phys. 128, 024105 (2008)
Article history
Received:
October 05 2007
Accepted:
October 31 2007
Citation
Johan Henriksson, Trond Saue, Patrick Norman; Quadratic response functions in the relativistic four-component Kohn-Sham approximation. J. Chem. Phys. 14 January 2008; 128 (2): 024105. https://doi.org/10.1063/1.2816709
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