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Four-component Hartree–Fock calculations of magnetic-field induced circular birefringence—Faraday effect—in noble gases and dihalogens
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Area della Ricerca, Pisa, Italy.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
2005 (English)In: The Journal of Chemical Physics, ISSN 1050-2947, Vol. 122, 074321- p.Article in journal (Refereed) Published
Abstract [en]

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.
Keyword [en]
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
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-12695DOI: 10.1063/1.1849167OAI: oai:DiVA.org:liu-12695DiVA: diva2:16869
Available from: 2007-10-30 Created: 2007-10-30 Last updated: 2013-11-25
In thesis
1. Time-dependent molecular properties in the optical and x-ray regions
Open this publication in new window or tab >>Time-dependent molecular properties in the optical and x-ray regions
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Time-dependent molecular properties are important for the experimental characterization of molecular materials. We show how these properties can be calculated, for optical and x-ray frequencies, using novel quantum chemical methods. For xray absorption there are important relativistic effects appearing, due to the high velocity electrons near the atomic nuclei. These effects are treated rigorously within the four-component static exchange approximation. We also show how electron correlation can be taken into account in the calculation of x-ray absorption spectra, in time-dependent density functional theory based on the complex polarization propagator approach. The methods developed have been applied to systems of experimental interest|molecules in the gas phase and adsorbed on metal surfaces. The effects of molecular vibrations have been take into account both within and beyond the harmonic approximation.

Place, publisher, year, edition, pages
Institutionen för fysik, kemi och biologi, 2007
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1131
Keyword
Quantum chemistry, molecular physics, x-ray spectroscopy, relativity
National Category
Other Physics Topics
Identifiers
urn:nbn:se:liu:diva-10125 (URN)978-91-85895-88-5 (ISBN)
Public defence
2007-10-23, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2007-10-30 Created: 2007-10-30 Last updated: 2009-04-26
2. Birefringences and X-ray absorption from relativistic and nonrelativistic quantum chemical methods
Open this publication in new window or tab >>Birefringences and X-ray absorption from relativistic and nonrelativistic quantum chemical methods
2005 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Application of quantum chemical methods for the prediction and interpretation of optical and X-ray experiments have been performed. X-ray absorption and X-ray photo-electron spectroscopy of pentacene in the gas phase has been studied using the static exchange approximation. A generalizat ion of the static exchange approximation, to the relativistic four-component realm is presented and applied to the H2S molecule. This generalization allows for a description of the effects the strong spin-orbit coupling in the core region of atoms. Two types of birefringences, Faraday effect and electric field gradient induced birefringence, a re calculated for small molecules in the gas phase, and the effects of relativity are considered for these nonlinear optical properties.

Place, publisher, year, edition, pages
Linköping: Linköpings universitet, 2005. 40 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1211
Series
LIU-TEK-LIC, 66
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-31976 (URN)17818 (Local ID)91-8545-772-8 (ISBN)17818 (Archive number)17818 (OAI)
Available from: 2009-10-09 Created: 2009-10-09 Last updated: 2013-11-25

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Ekström, UlfNorman, Patrick

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