Intermolecular charge transfer between heterocyclic oligomers. Effects of heteroatom and molecular packing on hopping transport in organic semiconductors

Geoffrey R. Hutchison, Mark A. Ratner, Tobin J. Marks

Research output: Contribution to journalArticle

341 Citations (Scopus)

Abstract

For electron or hole transfer between neighboring conducting polymer strands or oligomers, the intrinsic charge-transfer rate is dictated by the charge-resonance integral and by the reorganization energy due to geometric relaxation. To explain conduction anisotropy and other solid-state effects, a multivariate, systematic analysis of bandwidth as a function of intermolecular orientations is undertaken for a series of oligoheterocycles, using first-principles methods. While cofacial oligomers show the greatest bandwidths at a given intermolecular C-C contact distance, for a fixed center-to-center intermolecular distance, tilted π-stacking increases π-overlap (particularly for LUMO orbitals) and decreases electrostatic repulsion, yielding optimum tilt angles for packing of ∼40-60° at small intermolecular separations. The calculations also reveal that bandwidths and intrinsic mobilities of holes and electrons in conjugated oligoheterocycles can be quite comparable.

Original languageEnglish
Pages (from-to)16866-16881
Number of pages16
JournalJournal of the American Chemical Society
Volume127
Issue number48
DOIs
Publication statusPublished - Dec 7 2005

Fingerprint

Semiconductors
Semiconducting organic compounds
Oligomers
Charge transfer
Electrons
Bandwidth
Anisotropy
Static Electricity
Polymers
Multivariate Analysis
Conducting polymers
Electrostatics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{7519c39cdd4f48be9643b7ea50f511a3,
title = "Intermolecular charge transfer between heterocyclic oligomers. Effects of heteroatom and molecular packing on hopping transport in organic semiconductors",
abstract = "For electron or hole transfer between neighboring conducting polymer strands or oligomers, the intrinsic charge-transfer rate is dictated by the charge-resonance integral and by the reorganization energy due to geometric relaxation. To explain conduction anisotropy and other solid-state effects, a multivariate, systematic analysis of bandwidth as a function of intermolecular orientations is undertaken for a series of oligoheterocycles, using first-principles methods. While cofacial oligomers show the greatest bandwidths at a given intermolecular C-C contact distance, for a fixed center-to-center intermolecular distance, tilted π-stacking increases π-overlap (particularly for LUMO orbitals) and decreases electrostatic repulsion, yielding optimum tilt angles for packing of ∼40-60° at small intermolecular separations. The calculations also reveal that bandwidths and intrinsic mobilities of holes and electrons in conjugated oligoheterocycles can be quite comparable.",
author = "Hutchison, {Geoffrey R.} and Ratner, {Mark A.} and Marks, {Tobin J.}",
year = "2005",
month = "12",
day = "7",
doi = "10.1021/ja0533996",
language = "English",
volume = "127",
pages = "16866--16881",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "48",

}

TY - JOUR

T1 - Intermolecular charge transfer between heterocyclic oligomers. Effects of heteroatom and molecular packing on hopping transport in organic semiconductors

AU - Hutchison, Geoffrey R.

AU - Ratner, Mark A.

AU - Marks, Tobin J.

PY - 2005/12/7

Y1 - 2005/12/7

N2 - For electron or hole transfer between neighboring conducting polymer strands or oligomers, the intrinsic charge-transfer rate is dictated by the charge-resonance integral and by the reorganization energy due to geometric relaxation. To explain conduction anisotropy and other solid-state effects, a multivariate, systematic analysis of bandwidth as a function of intermolecular orientations is undertaken for a series of oligoheterocycles, using first-principles methods. While cofacial oligomers show the greatest bandwidths at a given intermolecular C-C contact distance, for a fixed center-to-center intermolecular distance, tilted π-stacking increases π-overlap (particularly for LUMO orbitals) and decreases electrostatic repulsion, yielding optimum tilt angles for packing of ∼40-60° at small intermolecular separations. The calculations also reveal that bandwidths and intrinsic mobilities of holes and electrons in conjugated oligoheterocycles can be quite comparable.

AB - For electron or hole transfer between neighboring conducting polymer strands or oligomers, the intrinsic charge-transfer rate is dictated by the charge-resonance integral and by the reorganization energy due to geometric relaxation. To explain conduction anisotropy and other solid-state effects, a multivariate, systematic analysis of bandwidth as a function of intermolecular orientations is undertaken for a series of oligoheterocycles, using first-principles methods. While cofacial oligomers show the greatest bandwidths at a given intermolecular C-C contact distance, for a fixed center-to-center intermolecular distance, tilted π-stacking increases π-overlap (particularly for LUMO orbitals) and decreases electrostatic repulsion, yielding optimum tilt angles for packing of ∼40-60° at small intermolecular separations. The calculations also reveal that bandwidths and intrinsic mobilities of holes and electrons in conjugated oligoheterocycles can be quite comparable.

UR - http://www.scopus.com/inward/record.url?scp=28844434139&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=28844434139&partnerID=8YFLogxK

U2 - 10.1021/ja0533996

DO - 10.1021/ja0533996

M3 - Article

C2 - 16316233

AN - SCOPUS:28844434139

VL - 127

SP - 16866

EP - 16881

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 48

ER -