### Abstract

A theoretical characterization of the potential energy surfaces of the singlet benzene excimer states derived from the B _{2u} monomer excited state has been performed using time-dependent density functional theory. The excited-state potential energy surfaces were initially characterized by computations along the parallel and perpendicular intermolecular translational coordinates. These calculations predict that the lowest excited state for parallel translation is bound with a minimum at 3.15 Å and with a binding energy of 0.46 eV, while the perpendicular translational coordinate was essentially found to be a repulsive state. At the calculated minimum distance, the effect of in-plane rotation, out-of-plane rotation, and slipped-parallel translation were examined. The rotational calculations predict that deviations from the D _{6h} geometry lead to a destabilization of the excimer state; however, small angular variations in the range of 0°-10° are predicted to be energetically feasible. The slipped-parallel translational calculations also predict a destabilizing effect on the excimer state and were found to possess barriers to this type of dissociation in the range of 0.50-0.61 eV. When compared to experimentally determined values for the benzene excimer energetics, the calculated values were found to be in semiquantitative agreement. Overall, this study suggests that the time-dependent density functional theory method can be used to characterize the potential energy surfaces and the energetics of aromatic excimers with reasonable accuracy.

Original language | English (US) |
---|---|

Pages (from-to) | 9174-9182 |

Number of pages | 9 |

Journal | Journal of Physical Chemistry A |

Volume | 109 |

Issue number | 40 |

DOIs | |

State | Published - Oct 13 2005 |

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### All Science Journal Classification (ASJC) codes

- Physical and Theoretical Chemistry

### Cite this

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*Journal of Physical Chemistry A*, vol. 109, no. 40, pp. 9174-9182. https://doi.org/10.1021/jp053445o

**Theoretical study of the benzene excimer using time-dependent density functional theory.** / Amicangelo, Jay.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Theoretical study of the benzene excimer using time-dependent density functional theory

AU - Amicangelo, Jay

PY - 2005/10/13

Y1 - 2005/10/13

N2 - A theoretical characterization of the potential energy surfaces of the singlet benzene excimer states derived from the B 2u monomer excited state has been performed using time-dependent density functional theory. The excited-state potential energy surfaces were initially characterized by computations along the parallel and perpendicular intermolecular translational coordinates. These calculations predict that the lowest excited state for parallel translation is bound with a minimum at 3.15 Å and with a binding energy of 0.46 eV, while the perpendicular translational coordinate was essentially found to be a repulsive state. At the calculated minimum distance, the effect of in-plane rotation, out-of-plane rotation, and slipped-parallel translation were examined. The rotational calculations predict that deviations from the D 6h geometry lead to a destabilization of the excimer state; however, small angular variations in the range of 0°-10° are predicted to be energetically feasible. The slipped-parallel translational calculations also predict a destabilizing effect on the excimer state and were found to possess barriers to this type of dissociation in the range of 0.50-0.61 eV. When compared to experimentally determined values for the benzene excimer energetics, the calculated values were found to be in semiquantitative agreement. Overall, this study suggests that the time-dependent density functional theory method can be used to characterize the potential energy surfaces and the energetics of aromatic excimers with reasonable accuracy.

AB - A theoretical characterization of the potential energy surfaces of the singlet benzene excimer states derived from the B 2u monomer excited state has been performed using time-dependent density functional theory. The excited-state potential energy surfaces were initially characterized by computations along the parallel and perpendicular intermolecular translational coordinates. These calculations predict that the lowest excited state for parallel translation is bound with a minimum at 3.15 Å and with a binding energy of 0.46 eV, while the perpendicular translational coordinate was essentially found to be a repulsive state. At the calculated minimum distance, the effect of in-plane rotation, out-of-plane rotation, and slipped-parallel translation were examined. The rotational calculations predict that deviations from the D 6h geometry lead to a destabilization of the excimer state; however, small angular variations in the range of 0°-10° are predicted to be energetically feasible. The slipped-parallel translational calculations also predict a destabilizing effect on the excimer state and were found to possess barriers to this type of dissociation in the range of 0.50-0.61 eV. When compared to experimentally determined values for the benzene excimer energetics, the calculated values were found to be in semiquantitative agreement. Overall, this study suggests that the time-dependent density functional theory method can be used to characterize the potential energy surfaces and the energetics of aromatic excimers with reasonable accuracy.

UR - http://www.scopus.com/inward/record.url?scp=27144551975&partnerID=8YFLogxK

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U2 - 10.1021/jp053445o

DO - 10.1021/jp053445o

M3 - Article

C2 - 16332027

AN - SCOPUS:27144551975

VL - 109

SP - 9174

EP - 9182

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 40

ER -