Quadratic response functions in the relativistic four-component Kohn-Sham approximation
2008 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 128, no 2, 024105- p.Article in journal (Refereed) Published
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 µ-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
Place, publisher, year, edition, pages
2008. Vol. 128, no 2, 024105- p.
density functional theory, eigenvalues and eigenfunctions, organic compounds, polarisability
IdentifiersURN: urn:nbn:se:liu:diva-12937DOI: 10.1063/1.2816709OAI: oai:DiVA.org:liu-12937DiVA: diva2:17486