Four-component Hartree–Fock calculations of magnetic-field induced circular birefringence—Faraday effect—in noble gases and dihalogens
2005 (English)In: The Journal of Chemical Physics, ISSN 1050-2947 (print), 1094-1622 (online), Vol. 122, 074321- p.Article in journal (Refereed) Published
Theeffects of relativity on the magnetic-field induced circular birefringence, orFaraday effect, in He, Ne, Ar, Xe, Rn, F2, Cl2,Br2, and I2 have been determined at the four-component Hartree–Focklevel of theory. A measure of the birefringence is givenby the Verdet constant, which is a third-order molecular propertyand thus relates to quadratic response functions. A fully analyticalnonlinear polarization propagator approach is employed. The results are gaugeinvariant as a consequence of the spatial symmetries in themolecular systems. The calculations include electronic as well as vibrationalcontributions to the property. Comparison with experiment is made forHe, Ne, Ar, Xe, and Cl2, and, apart from neon,the theoretical values of the Verdet constant are within 10%of the experimental ones. The inclusion of nonrelativistically spin-forbidden excitationsin the propagator parametrization has significant effects on the dispersionin general, but such effects are in the general caselargely explained by the use of a resonant-divergent propagator theory.In the present work we do, however, observe noticeable relativisticcorrections to the Verdet constant in the off-resonant regions forsystems with light elements (F2 and Cl2), and nonrelativistic resultsfor the Verdet constant of Br2 are in error by25% in the low-frequency region. ©2005 American Institute of Physics.
Place, publisher, year, edition, pages
2005. Vol. 122, 074321- p.
HF calculations, birefringence, helium, neon, argon, xenon, radon, fluorine, chlorine, bromine, iodine, Faraday effect, polarisation, relativistic corrections, vibrational states, excited states, resonant states, magnetic fields
IdentifiersURN: urn:nbn:se:liu:diva-12695DOI: 10.1063/1.1849167OAI: oai:DiVA.org:liu-12695DiVA: diva2:16869