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 language | English |
|---|---|
| Pages (from-to) | 16866-16881 |
| Number of pages | 16 |
| Journal | Journal of the American Chemical Society |
| Volume | 127 |
| Issue number | 48 |
| DOIs | |
| Publication status | Published - Dec 7 2005 |
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ASJC Scopus subject areas
- Chemistry(all)
Cite this
Intermolecular charge transfer between heterocyclic oligomers. Effects of heteroatom and molecular packing on hopping transport in organic semiconductors. / Hutchison, Geoffrey R.; Ratner, Mark A.; Marks, Tobin J.
In: Journal of the American Chemical Society, Vol. 127, No. 48, 07.12.2005, p. 16866-16881.Research output: Contribution to journal › Article
}
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.
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U2 - 10.1021/ja0533996
DO - 10.1021/ja0533996
M3 - Article
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 -