An Effective Core Potential ab Initio Study of Electronic Structure and Bandwidth-Charge Transport Relationships in Low-Dimensional, Partially Oxidized Palladium Glyoximates

Santo Di Bella, Giuseppe Lanza, Ignazio Fragalà, Tobin J. Marks, Mark A. Ratner

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Ab initio calculations on cofacial dimers of palladium bis(glyoximates) are reported and are used to rationalize the temperature-dependent conductivity of the low-dimensional, partially-oxidized material Pd(dpg)20.20+(I5)0.20 (dpg = diphenylglyoximato). The band structure near the Fermi level is dominated by two bands, of b3g and au symmetry in the dimer, that arise from the ligand π orbitais. Near the observed (dpg)2Pd-Pd(dpg)2 staggering angle (90°), the b3g bandwidth is zero, and the au band exhibits sharp variations with librational (twist) motion about the intermolecular Pd-Pd vector. This in turn, combined with the narrow bandwidth (calculated to be ~0.60 eV in a tight-binding model) implies that the electronic states are localized and that the material should be a hopping semiconductor rather than a molecular metal, in agreement with experiment.

Original languageEnglish
Pages (from-to)1983-1987
Number of pages5
JournalInorganic Chemistry
Issue number8
Publication statusPublished - Mar 1 1995


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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