Time-dependent density functional theory for non-linear properties of open-shell systems
2007 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 127, no 11, 114101- p.Article in journal (Refereed) Published
This paper presents response theory based on a spin-restricted Kohn-Sham formalism for computation of time-dependent and time-independent nonlinear properties of molecules with a high spin ground state. The developed approach is capable to handle arbitrary perturbations and constitutes an efficient procedure for evaluation of electric, magnetic, and mixed properties. Apart from presenting the derivation of the proposed approach, we show results from illustrating calculations of static and dynamic hyperpolarizabilities of small Si(3n+1)H(6n+3) (n=0,1,2) clusters which mimic Si(111) surfaces with dangling bond defects. The results indicate that the first hyperpolarizability tensor components of Si(3n+1)H(6n+3) have an ordering compatible with the measurements of second harmonic generation in SiO2/Si(111) interfaces and, therefore, support the hypothesis that silicon surface defects with dangling bonds are responsible for this phenomenon. The results exhibit a strong dependence on the quality of basis set and exchange-correlation functional, showing that an appropriate set of diffuse functions is required for reliable predictions of the first hyperpolarizability of open-shell compounds.
Place, publisher, year, edition, pages
2007. Vol. 127, no 11, 114101- p.
IdentifiersURN: urn:nbn:se:kth:diva-7069DOI: 10.1063/1.2768357ISI: 000249667400007ScopusID: 2-s2.0-34648828833OAI: oai:DiVA.org:kth-7069DiVA: diva2:11971
QC 201008112007-05-112007-05-112011-11-07Bibliographically approved