On the evaluation of quadratic response functions at the four-component Hartree-Fock level: Nonlinear polarization and two-photon absorption in bromo- and iodobenzen
2006 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 124, no 21, 214311- p.Article in journal (Refereed) Published
The nonlinear polarization and two-photon absorption parameters have been determined for dibromo- and di-iodobenzene in their meta- and ortho-conformations and with relativistic effects accounted for to a varying degree. By exclusion of small component integrals in the calculations of the first-order hyperpolarizability, results within 1% of fully relativistic four-component Hartree-Fock values are obtained at a cost of 8.7 times the corresponding nonrelativistic calculations. It is shown that the nonlinear absorption in bromobenzene (and even more so in iodobenzene) is broad banded due to spin-orbit interactions among the excited states, and nonrelativistic and scalar relativistic calculations are not to be used in this case.
Place, publisher, year, edition, pages
2006. Vol. 124, no 21, 214311- p.
organic compounds, HF calculations, two-photon processes, relativistic corrections, polarisability, spin-orbit interactions, excited states
IdentifiersURN: urn:nbn:se:liu:diva-13999DOI: 10.1063/1.2204604OAI: oai:DiVA.org:liu-13999DiVA: diva2:22429