Resistivity mechanisms in phthalocyanine-based linear-chain and polymeric conductors: Variation of bandwidth with geometry

William J. Pietro, Tobin J Marks, Mark A Ratner

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Abstract

The Wolfsberg-Helmholtz correlation between overlap and exchange integrals has been employed along with a tight-binding band scheme to study the effects of various geometric distortions on the calculated bandwidths of the phthalocyanine-based polymeric conductor [Si(Pc)O]n (Pc = phthalocyaninato). Importantly, the Wolfsberg-Helmholtz parameterization constant has been calculated for the overlapping, cofacial π systems in a dimeric fragment of the polymer by using coulomb and exchange integrals and molecular wave functions derived from an all-electron ab initio DVM-Xα calculation on the monomeric phthalocyanine subunit. The results indicate that bandwidths calculated by using a simple Wolfsberg-Helmholtz type correlation with properly calculated parameters are in remarkably good agreement with those calculated from DVM-Xα. Consequently, the determination of phonon- and libron-induced modulations of polymeric bandwidths in such conductors requires high-level electronic structure calculations only for the monomeric subunits. The phthalocyanine motions parallel to the Si-O-Si backbone and the rotations about this backbone appear to dominate the resistivity, since their electron/vibration coupling constants are large.

Original languageEnglish
Pages (from-to)5387-5391
Number of pages5
JournalJournal of the American Chemical Society
Volume107
Issue number19
Publication statusPublished - 1985

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Digital voltmeters
Bandwidth
Geometry
Phonons
Electrons
Wave functions
Vibration
Parameterization
Electronic structure
Polymers
Modulation
phthalocyanine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "The Wolfsberg-Helmholtz correlation between overlap and exchange integrals has been employed along with a tight-binding band scheme to study the effects of various geometric distortions on the calculated bandwidths of the phthalocyanine-based polymeric conductor [Si(Pc)O]n (Pc = phthalocyaninato). Importantly, the Wolfsberg-Helmholtz parameterization constant has been calculated for the overlapping, cofacial π systems in a dimeric fragment of the polymer by using coulomb and exchange integrals and molecular wave functions derived from an all-electron ab initio DVM-Xα calculation on the monomeric phthalocyanine subunit. The results indicate that bandwidths calculated by using a simple Wolfsberg-Helmholtz type correlation with properly calculated parameters are in remarkably good agreement with those calculated from DVM-Xα. Consequently, the determination of phonon- and libron-induced modulations of polymeric bandwidths in such conductors requires high-level electronic structure calculations only for the monomeric subunits. The phthalocyanine motions parallel to the Si-O-Si backbone and the rotations about this backbone appear to dominate the resistivity, since their electron/vibration coupling constants are large.",
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T2 - Variation of bandwidth with geometry

AU - Pietro, William J.

AU - Marks, Tobin J

AU - Ratner, Mark A

PY - 1985

Y1 - 1985

N2 - The Wolfsberg-Helmholtz correlation between overlap and exchange integrals has been employed along with a tight-binding band scheme to study the effects of various geometric distortions on the calculated bandwidths of the phthalocyanine-based polymeric conductor [Si(Pc)O]n (Pc = phthalocyaninato). Importantly, the Wolfsberg-Helmholtz parameterization constant has been calculated for the overlapping, cofacial π systems in a dimeric fragment of the polymer by using coulomb and exchange integrals and molecular wave functions derived from an all-electron ab initio DVM-Xα calculation on the monomeric phthalocyanine subunit. The results indicate that bandwidths calculated by using a simple Wolfsberg-Helmholtz type correlation with properly calculated parameters are in remarkably good agreement with those calculated from DVM-Xα. Consequently, the determination of phonon- and libron-induced modulations of polymeric bandwidths in such conductors requires high-level electronic structure calculations only for the monomeric subunits. The phthalocyanine motions parallel to the Si-O-Si backbone and the rotations about this backbone appear to dominate the resistivity, since their electron/vibration coupling constants are large.

AB - The Wolfsberg-Helmholtz correlation between overlap and exchange integrals has been employed along with a tight-binding band scheme to study the effects of various geometric distortions on the calculated bandwidths of the phthalocyanine-based polymeric conductor [Si(Pc)O]n (Pc = phthalocyaninato). Importantly, the Wolfsberg-Helmholtz parameterization constant has been calculated for the overlapping, cofacial π systems in a dimeric fragment of the polymer by using coulomb and exchange integrals and molecular wave functions derived from an all-electron ab initio DVM-Xα calculation on the monomeric phthalocyanine subunit. The results indicate that bandwidths calculated by using a simple Wolfsberg-Helmholtz type correlation with properly calculated parameters are in remarkably good agreement with those calculated from DVM-Xα. Consequently, the determination of phonon- and libron-induced modulations of polymeric bandwidths in such conductors requires high-level electronic structure calculations only for the monomeric subunits. The phthalocyanine motions parallel to the Si-O-Si backbone and the rotations about this backbone appear to dominate the resistivity, since their electron/vibration coupling constants are large.

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