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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Abstract

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 orbitals. 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
Volume34
Issue number8
Publication statusPublished - 1995

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Palladium
Dimers
Electronic structure
Charge transfer
palladium
electronic structure
bandwidth
Bandwidth
Electronic states
Fermi level
dimers
Band structure
librational motion
staggering
Metals
Semiconductor materials
Ligands
orbitals
conductivity
ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "An effective core potential ab initio study of electronic structure and bandwidth - Charge transport relationships in low-dimensional, partially oxidized palladium glyoximates",
abstract = "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 orbitals. 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.",
author = "{Di Bella}, Santo and Giuseppe Lanza and Ignazio Fragal{\`a} and Marks, {Tobin J} and Ratner, {Mark A}",
year = "1995",
language = "English",
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pages = "1983--1987",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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TY - JOUR

T1 - An effective core potential ab initio study of electronic structure and bandwidth - Charge transport relationships in low-dimensional, partially oxidized palladium glyoximates

AU - Di Bella, Santo

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio

AU - Marks, Tobin J

AU - Ratner, Mark A

PY - 1995

Y1 - 1995

N2 - 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 orbitals. 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.

AB - 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 orbitals. 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.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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