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Can density functional methods be used for open-shell actinide molecules? Comparison with multiconfigurational

Carine Clavaguéra-Sarrio1, Valérie Vallet, Daniel Maynau

  • 1Laboratoire de Physique Quantique, UMR 5626, IRSAMC, Université Paul Sabatier, 118 route de Narbonne, 31 062 Toulouse Cedex 4, France. cclavaguera@cea.fr

The Journal of Chemical Physics
|September 9, 2004
PubMed
Summary

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This study investigates plutonium compounds PuO(2)(2+) and PuN(2) using advanced computational methods. Results clarify electronic ground states and excited states, highlighting the importance of spin-orbit coupling for accurate spectral assignments.

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Spectroscopy

Background:

  • Accurate theoretical descriptions of actinide compounds are crucial for understanding their chemical behavior.
  • Previous studies on plutonium compounds like PuO(2)(2+) and PuN(2) have presented differing electronic ground state assignments.
  • The influence of spin-orbit coupling on electronic structure and spectra requires careful consideration for heavy elements.

Purpose of the Study:

  • To investigate the electronic structures, geometries, and vibrational frequencies of isoelectronic PuO(2)(2+) and PuN(2).
  • To compare the performance of density functional theory (DFT) and multiconfigurational ab initio methods, including spin-orbit effects.
  • To clarify the electronic ground state assignment for PuN(2) and provide a comprehensive analysis of electronic transitions.

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Main Methods:

  • Density Functional Theory (DFT) calculations.
  • Multiconfigurational ab initio methods, including Complete Active Space Second-Order Perturbation Theory (CASPT2) and variational difference-dedicated configuration interaction.
  • Inclusion of spin-orbit coupling using an effective uncontracted spin-orbit configuration-interaction method.

Main Results:

  • The electronic ground state for both PuO(2)(2+) and PuN(2) is identified as the Omega=4 component of (3)H(g), correcting a previous assignment for PuN(2).
  • Spin-orbit effects have a minor impact on ground-state geometries and vibrational frequencies but significantly alter the distribution of excited electronic states.
  • Both CASPT2 and DFT methods accurately reproduce the experimental antisymmetric stretching frequency of PuN(2), with generalized gradient approximation DFT formulations showing better agreement than hybrid versions.

Conclusions:

  • Multireference methods incorporating spin-orbit coupling are essential for unambiguous assignment of electronic ground states and spectra in these systems.
  • DFT methods offer a reasonable description of ground-state properties for these open-shell systems, including structural and vibrational characteristics.
  • The study provides a comparative analysis of ground-state properties for related actinide dioxides and dinitrogen compounds (UO(2)(2+), UN(2), UO(2), PuO(2)(2+), and PuN(2)).