Change search
ReferencesLink to record
Permanent link

Direct link
Four-component Hartree-Fock calculations of magnetic-field induced circular birefringence - Faraday effect - In noble gases and dihalogens
2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 122, no 7, 074321Article in journal (Refereed) Published
Abstract [en]

The effects of relativity on the magnetic-field induced circular birefringence, or Faraday effect, in He, Ne, Ar, Xe, Rn, F 2, Cl 2, Br 2, and I 2 have been determined at the four-component Hartree-Fock level of theory. A measure of the birefringence is given by the Verdet constant, which is a third-order molecular property and thus relates to quadratic response functions. A fully analytical nonlinear polarization propagator approach is employed. The results are gauge invariant as a consequence of the spatial symmetries in the molecular systems. The calculations include electronic as well as vibrational contributions to the property. Comparison with experiment is made for He, Ne, Ar, Xe, and Cl 2, and, apart from neon, the theoretical values of the Verdet constant are within 10% of the experimental ones. The inclusion of nonrelativistically spin-forbidden excitations in the propagator parametrization has significant effects on the dispersion in general, but such effects are in the general case largely explained by the use of a resonant-divergent propagator theory. In the present work we do, however, observe noticeable relativistic corrections to the Verdet constant in the off-resonant regions for systems with light elements (F 2 and Cl 2), and nonrelativistic results for the Verdet constant of Br 2 are in error by 25% in the low-frequency region.

Place, publisher, year, edition, pages
2005. Vol. 122, no 7, 074321
Keyword [en]
Faraday effects, Hartree-Fock calculations, Light elements, Verdet constant, Birefringence, Error analysis, Magnetic fields, Molecular dynamics, Molecular vibrations, Polarization, Inert gases
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-198791DOI: 10.1063/1.1849167ScopusID: 2-s2.0-22944442226OAI: oai:DiVA.org:kth-198791DiVA: diva2:1058932
Note

References: Faraday, M., (1846) Philos. Mag., 28, p. 294; Verdet, E., (1854) Compt. Rend., 39, p. 548; Buckingham, A.D., (1966) Annu. Rev. Phys. Chem., 17, p. 399; Cadwell, D., Eyring, H., (1971) The Theory of Optical Activity, , Wiley-Interscience, New York; Wagnière, G.H., (1993) Linear and Nonlinear Optical Properties of Molecules, , Verlag Helvetica Chimica Acta, Basel; Barron, L.D., (1982) Molecular Light Scattering and Optical Activity, , Cambridge University Press, Cambridge; Parkinson, W.A., (1997) Int. J. Quantum Chem., 64, p. 599; Parkinson, W.A., (1993) J. Chem. Phys., 98, p. 487; Jaszunski, M., (1994) Chem. Phys. Lett., 222, p. 263; Coriani, S., (1997) Chem. Phys. Lett., 281, p. 445; Coriani, S., (1998) Chem. Phys. Lett., 293, p. 324; Norman, P., (2004) J. Chem. Phys., 121, p. 6145; Norman, P., (2002) J. Chem. Phys., 116, p. 6914; Jansik, B., (2003) J. Mol. Struct.: THEOCHEM, 633, p. 237; Rizzo, A., (2003) J. Mol. Struct.: THEOCHEM, 633, p. 163; Saue, T., (2002) Relativistic Electronic Structure Theory - Part 1: Fundamentals, , edited by, P. Schwerdtfeger, (Elsevier, Amsterdam); Merzbacher, E., (1970) Quantum Mechanics, 2nd Ed., , Wiley, New York; Bishop, D.M., (1990) Mol. Phys., 71, p. 667; Huber, K.P., Herzberg, G., (1979) Molecular Spectra and Molecular Structure, Vol. IV: Constants of Diatomic Molecules, 4. , Van Nostrand Reinhold, New York; Kaupp, M., (1991) J. Am. Chem. Soc., 113, p. 6012; Becke, A., (1993) J. Chem. Phys., 98, p. 5648; Sadlej, A.D., (1991) Theor. Chim. Acta, 79, p. 123; Sadlej, A.D., (1991) Theor. Chim. Acta, 81, p. 45; Sadlej, A.D., (1992) Theor. Chim. Acta, 81, p. 339; Woon, D.E., (1993) J. Chem. Phys., 98, p. 1358; Huzinaga, S., (1993) Chem. Phys. Lett., 212, p. 260; Andersson, K., Blomberg, M.R.A., Fülscher, M.P., (1997) MOLCAS Version 4, , Lund University, Sweden; Helgaker, T., Jensen, H.J.Aa., Jørgensen, P., (2001) DALTON, A Molecular Electronic Structure Program, Release 1.2; Jensen, H.J.Aa., Saue, T., Visscher, L., (2004) DIRAC, A Relativistic Ab Initio Electronic Structure Program, Release dirac04.0, , with contributions from V. Bakken, E. Eliav, T. Enevoldsen et al; H.J. Aa. Jensen and T. Saue (unpublished)Ingersoll, L., (1954) J. Opt. Soc. Am., 44, p. 566; Landolt, H.H., Börnstein, R., (1995) New Series II: Atomic and Molecular Physics, , Springer, Berlin; Dyall, K., (1994) J. Chem. Phys., 100, p. 2118; Douglas, M., (1974) Ann. Phys., 82, p. 89; Jansen, G., (1989) Phys. Rev. A, 39, p. 6016

Available from: 2016-12-21 Created: 2016-12-21 Last updated: 2016-12-21

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Norman, P.
In the same journal
Journal of Chemical Physics
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

Altmetric score

ReferencesLink to record
Permanent link

Direct link