Relativistic electronic structure of staggered and eclipsed conformations of octachlorodiosmate(III)

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Abstract

Symmetry-adapted angular momentum basis functions have been generated for the D4d* and D4h* molecular double point groups. These basis functions are used to obtain the relativistic molecular orbitals for the staggered (D4d) and eclipsed (D4h) rotameric geometries of octachlorodiosmate(III) via the self-consistent field Dirac Scattered-Wave (SCF-DSW) method. Double-point-group symmetry arguments and relativistic molecular orbital calculations for the Os2Cl8 2- ions indicate that the molecular orbitals involving the σ, iπ, δ, and δ* metal-metal bond components remain nondegenerate in both conformations. Spin-orbit interaction splits the π bond component of both conformers by about 0.35 eV and removes the orbital degeneracy involving the δ and δ* bond components of the staggered conformer. Double-point-group arguments and the results of DSW calculations on the staggered conformer allow us to reassign the two lowest absorption bands seen in the visible spectrum as being primarily metal-metal based.

Original languageEnglish
Pages (from-to)7239-7244
Number of pages6
JournalJournal of Physical Chemistry
Volume95
Issue number19
Publication statusPublished - 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

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