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 language | English |
|---|---|
| Pages (from-to) | 5387-5391 |
| Number of pages | 5 |
| Journal | Journal of the American Chemical Society |
| Volume | 107 |
| Issue number | 19 |
| Publication status | Published - 1985 |
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ASJC Scopus subject areas
- Chemistry(all)
Cite this
Resistivity mechanisms in phthalocyanine-based linear-chain and polymeric conductors : Variation of bandwidth with geometry. / Pietro, William J.; Marks, Tobin J; Ratner, Mark A.
In: Journal of the American Chemical Society, Vol. 107, No. 19, 1985, p. 5387-5391.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Resistivity mechanisms in phthalocyanine-based linear-chain and polymeric conductors
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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M3 - Article
AN - SCOPUS:0000202996
VL - 107
SP - 5387
EP - 5391
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 19
ER -