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The molecular electric quadrupole moment and electric field gradient induced birefringence (Buckingham effect) of Cl2
Istituto per i Processi Chimico-Fisici del CNR, Area della Ricerca, Pisa, Italy.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics . Linköping University, The Institute of Technology.
Istituto per i Processi Chimico-Fisici del CNR, Area della Ricerca, Pisa, Italy.
Dipartimento di Scienze Chimiche, Università degli Studi di Trieste, Trieste, Italy.
2004 (English)In: Journal of Computational Methods in Sciences and Engineering, ISSN 1472-7978, Vol. 4, no 3, 365-380 p.Article in journal (Refereed) Published
Abstract [en]

An ab initio investigation of the molecular properties rationalizing the electric-field-gradient induced birefringence (Buckingham effect) for Cl_2 is presented. The quadrupole moment is determined using hierarchies of basis sets and wavefunction models. The electric dipole polarizability, the dipole - dipole - quadrupole and dipole - dipole - magnetic dipole hyperpolarizabilities are determined exploiting a Coupled Cluster Singles and Doubles (CCSD) response approach. The properties are zero-point vibrationally averaged, and the contribution of excited ro-vibrational states accounted for. To this end, the interatomic ^1Σ_g^+ ground state potential has been computed at CCSD plus perturbative triples - CCSD(T) - level employing a large augmented correlation consistent basis set. The effect of relativity is estimated at the Dirac-Hartree-Fock level. Our best value for the quadrupole moment of Cl_2 is (2.327 ± 0.010) au and it is in excellent agreement with experiment which, after revision and dependent on the procedure employed for correcting the original estimate of (2.24 ± 0.04) au of Graham et al., [Mol. Phys., 93, 49, (1998)], ranges from (2.31 ± 0.04) au to (2.36 ± 0.04) au.

Place, publisher, year, edition, pages
2004. Vol. 4, no 3, 365-380 p.
Keyword
molecular quadrupole moment, birefringence, electric field gradient, electric dipole (hyper)polarizabilities, coupled cluster theory, relativistic effects, molecular vibrations
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-12696OAI: oai:DiVA.org:liu-12696DiVA: diva2:16870
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, Ulf

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