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Traitement de l'interaction spin-orbite en chimie quantique et application à la réactivité des complexes d'actinides
Stockholm University, Faculty of Science, Department of Physics.
2005 (French)Doctoral thesis, monograph (Other academic)Alternative title
Treatment of spin-orbit interaction in quantum chemistry and applications in actinide chemistry (English)
Abstract [en]

The recent methodological developments and the advent of faster computers enable nowadays to investigate theoretically the chemical reactivity of heavy element complexes. As an example we can mention actinide chemistry which is involved in the separation of nuclear wastes. In this case the relativistic effects induced by the heavy nuclei have to be calculated accurately. If the so-called scalar relativistic effects can be treated in electronic structure calculations with the same cost as non relativistic calculations, the treatment of spin-orbit coupling is however rather expensive. Pertinent approximations have then to be investigated. The present exchange program (Thèse en cotutelle) thesis, between Paul Sabatier University (Toulouse) and Stockholm University, focuses mainly on this problem.

The first part is devoted to the development of one-component extraction procedures of relativistic pseudopotentials from reference all-electron four-component calculations. A new extraction procedure of the spin-orbit pseudopotential has been proposed and successfully tested on the halogens and the tellurium atom. Moreover, an uncontracted spin-orbit CI adapted version of the method has been formulated by means of the perturbation theory formalism. The atomic results on iodine demonstrate the validity of such an approach for an accurate computation of the spin-orbit coupling in a pseudopotential one-component scheme. The introduction of atomic core effects in "shape-consistent" pseudopotentials is finally discussed.

The second part of this work is focused on applications as well as methodology. The electron transfer between actinyle complexes in solution, for which few experimental data are available, has been investigated by means of quantum chemical methods. Our results have shown similarities between uranium and neptunium complexes. From a methodological point of view, the tricky problem of solvent effects has been discussed. Moreover we have shown, using the EPCISO program implemented in Toulouse, that one-component approaches are well adapted to the calculation of spin-orbit coupling for early actinide complexes.

Place, publisher, year, edition, pages
Stockholm: Fysikum , 2005. , 232 p.
Keyword [en]
quantum chemistry, actinides, charge transfer reactions, spin-orbit effects
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-614OAI: oai:DiVA.org:su-614DiVA: diva2:196086
Public defence
2005-09-09, École Doctorale de Physique, Université Paul Sabatier, Toulouse, 13:00
Opponent
Supervisors
Available from: 2005-08-18 Created: 2005-08-18Bibliographically approved
List of papers
1. Atomic spin-orbit pseudopotential definition and its relation to the different relativistic approximations
Open this publication in new window or tab >>Atomic spin-orbit pseudopotential definition and its relation to the different relativistic approximations
2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 123Article in journal (Refereed) Published
Abstract [en]

A critical analysis of usual shape-consistent spin-orbit pseudopotential extraction procedures is presented, considering the basic requirements of the atomic pseudopotentials. It is based on a perturbative analysis of both reference all-electron Dirac–Coulomb and pseudopotential calculations by means of the formalism developed by Lindgren and Morrisson. In the light of this analysis, we propose a new hybrid extraction of spin-orbit pseudopotentials, taking advantage of both shape-consistent and energy-consistent procedures. These new pseudopotentials are extracted and checked for the ground state of the halogens.

Place, publisher, year, edition, pages
American Institute of Physics, 2005
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-23948 (URN)10.1063/1.1942467 (DOI)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18 Last updated: 2017-12-13Bibliographically approved
2. Extraction of shape-consistent spin-orbit pseudopotential from an effective spin-orbit parameter and application to the tellurium atom
Open this publication in new window or tab >>Extraction of shape-consistent spin-orbit pseudopotential from an effective spin-orbit parameter and application to the tellurium atom
2006 (English)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 106, no 3, 764-771 p.Article in journal (Refereed) Published
Abstract [en]

A hybrid procedure to extract spin-orbit pseudo-potentials is proposed, taking information from both the orbital shape in the valence region and the atomic spin-orbit splitting. An effective atomic spin-orbit parameter is derived from a Dirac–Coulomb–Fock reference atomic calculation and is then used to extract the spin-orbit pseudo-potential. This method is tested for the ground-state configuration (5s25p4) of the tellurium atom.

Place, publisher, year, edition, pages
Wiley Periodicals, 2006
Keyword
spin-orbit coupling;pseudo-potential theory;shape-consistent extraction procedure;energy-consistent extraction procedure;tellurium
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:su:diva-23949 (URN)10.1002/qua.20840 (DOI)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18 Last updated: 2017-12-13Bibliographically approved
3. On the accuracy of one-component pseudopotential spin-orbit calculations
Open this publication in new window or tab >>On the accuracy of one-component pseudopotential spin-orbit calculations
2005 (English)In: Journal of Chemical Physics, Vol. 123, no 16, 164105-164115 p.Article in journal (Refereed) Published
Abstract [en]

Improvements on current one-component extraction procedures of spin-orbit pseudopotentials are investigated for high accuracy computation of spin-orbit coupling energies. By means of the perturbation-theory formalism we first show that spin-orbit pseudopotentials, extracted at the one-component self-consistent-field level from a reference all-electron Dirac-Coulomb or Dirac-Coulomb-Breit calculation, include valence spin-orbit polarization and relaxation effects. As a consequence the use of these pseudopotentials in uncontracted spin-orbit configuration interaction (CI) with singles from the reference ground-state configuration gives rise to double counting of these spin-orbit effects. Two new methods that avoid such double counting have been investigated. The first, so-called “explicit” method, calculates explicitly, by means of a four-component spin-orbit CI, the double-counted spin-orbit effects and removes them from the pseudopotentials. Due to the nonadditivity of the core and valence spin-orbit effects as well as the so-called “pseudovariational collapse,” this method is shown to be cumbersome. In the second “implicit” method the spin-orbit pseudopotential is extracted at the spin-orbit polarized and relaxed level by means of a single-excitation spin-orbit CI calculation. Atomic tests on iodine demonstrate the ability of the latter method to solve the double-counting problem.

Keyword
*PSEUDOPOTENTIAL method *PARTICLES (Nuclear physics) *HALOGENS *IODINE *POTENTIAL theory (Physics) *ELECTRONS
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-23950 (URN)10.1063/1.2072927 (DOI)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18 Last updated: 2010-09-10Bibliographically approved
4. An analysis of core effects on shape-consistent pseudopotentials
Open this publication in new window or tab >>An analysis of core effects on shape-consistent pseudopotentials
Show others...
2004 In: Journal of Chemical Physics, ISSN 0021-9606, Vol. 121, no 18, 8687-8699 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23951 (URN)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18Bibliographically approved
5. Electron transfer in Uranyl(VI)-Uranyl(V) complexes in solution
Open this publication in new window or tab >>Electron transfer in Uranyl(VI)-Uranyl(V) complexes in solution
Show others...
2004 In: Journal of the American Chemical Society, ISSN 0002-7863, Vol. 126, no 31, 9801 -9808 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23952 (URN)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18Bibliographically approved
6. Electron transfer in Neptunyl(VI)-Neptunyl(V) complexes in solution
Open this publication in new window or tab >>Electron transfer in Neptunyl(VI)-Neptunyl(V) complexes in solution
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2005 In: The Journal Of Physical Chemistry A, ISSN 1089-5639, Vol. 109, no 22, 4950-4956 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23953 (URN)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18Bibliographically approved
7. Spin-orbit effects in electron transfer in Neptunyl(VI)-Neptunyl(V) complexes in solution
Open this publication in new window or tab >>Spin-orbit effects in electron transfer in Neptunyl(VI)-Neptunyl(V) complexes in solution
Show others...
2005 In: The Journal Of Physical Chemistry A, ISSN 1089-5639, Vol. 109, no 22, 4957-4960 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23954 (URN)
Note
Part of urn:nbn:se:su:diva-614Available from: 2005-08-18 Created: 2005-08-18Bibliographically approved

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