### Abstract

The electronic properties of thiophene oligomers (nT, n=2-8) have been investigated in the lowest excited triplet state. Theoretical calculations of the zero field splitting parameters and of the π-electron spin density have been performed and compared with previous experimental EPR results. The calculations are based on a simple π-electron (one-electron-per-site) model including electron-electron interaction at the extended Hubbard level. Optimized bond lengths result from making them self-consistent to the corresponding bond orders via Coulson's relationship. The calculated D values decrease from D=0.0959 cm^{-1} for n=2 to D=0.0597 cm^{-1} for n=8, in agreement with EPR data. The measured as well as the calculated E values are rather small. Furthermore, we found that ZFS parameters are affected by the torsion angles between the thiophene rings. The chain length dependence of D can be rationalized comparing π-electron spin density calculations and computed bond length distortions. These clearly indicate that the triplet excitation reaches a finite extension over about four thiophene rings.

Original language | English |
---|---|

Pages (from-to) | 4441-4447 |

Number of pages | 7 |

Journal | The Journal of Chemical Physics |

Volume | 105 |

Issue number | 11 |

Publication status | Published - 1996 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of Chemical Physics*,

*105*(11), 4441-4447.

**Zero-field-splitting and π-electron spin densities in the lowest excited triplet state of oligothiophenes.** / Bennati, M.; Németh, K.; Surján, P.; Mehring, M.

Research output: Contribution to journal › Article

*The Journal of Chemical Physics*, vol. 105, no. 11, pp. 4441-4447.

}

TY - JOUR

T1 - Zero-field-splitting and π-electron spin densities in the lowest excited triplet state of oligothiophenes

AU - Bennati, M.

AU - Németh, K.

AU - Surján, P.

AU - Mehring, M.

PY - 1996

Y1 - 1996

N2 - The electronic properties of thiophene oligomers (nT, n=2-8) have been investigated in the lowest excited triplet state. Theoretical calculations of the zero field splitting parameters and of the π-electron spin density have been performed and compared with previous experimental EPR results. The calculations are based on a simple π-electron (one-electron-per-site) model including electron-electron interaction at the extended Hubbard level. Optimized bond lengths result from making them self-consistent to the corresponding bond orders via Coulson's relationship. The calculated D values decrease from D=0.0959 cm-1 for n=2 to D=0.0597 cm-1 for n=8, in agreement with EPR data. The measured as well as the calculated E values are rather small. Furthermore, we found that ZFS parameters are affected by the torsion angles between the thiophene rings. The chain length dependence of D can be rationalized comparing π-electron spin density calculations and computed bond length distortions. These clearly indicate that the triplet excitation reaches a finite extension over about four thiophene rings.

AB - The electronic properties of thiophene oligomers (nT, n=2-8) have been investigated in the lowest excited triplet state. Theoretical calculations of the zero field splitting parameters and of the π-electron spin density have been performed and compared with previous experimental EPR results. The calculations are based on a simple π-electron (one-electron-per-site) model including electron-electron interaction at the extended Hubbard level. Optimized bond lengths result from making them self-consistent to the corresponding bond orders via Coulson's relationship. The calculated D values decrease from D=0.0959 cm-1 for n=2 to D=0.0597 cm-1 for n=8, in agreement with EPR data. The measured as well as the calculated E values are rather small. Furthermore, we found that ZFS parameters are affected by the torsion angles between the thiophene rings. The chain length dependence of D can be rationalized comparing π-electron spin density calculations and computed bond length distortions. These clearly indicate that the triplet excitation reaches a finite extension over about four thiophene rings.

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M3 - Article

VL - 105

SP - 4441

EP - 4447

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

ER -