Title

Preresonance Raman Spectrum of the C13H9 Fluorene-like Radical

ACS Citation

Szczepanski, J.; Banisaukas, J.; Vala, M.; Hirata, S.; Bartlett, R. J.; Head-Gordon, M. Vibrational and Electronic Spectroscopy of the Fluorene Cation. J. Phys. Chem. A 2002b, 106 (1), 63–73.

Abstract

The neutral open-shell species C13H9 formed from fluorene, C13H10, by low-energy electron bombardment and by ultraviolet photolysis in an argon matrix at 12 K has been studied via preresonance Raman, infrared, and ultraviolet/visible spectroscopy. Density functional theory calculations (B3LYP/6-31G(d,p)) of the CH bond energies of neutral fluorene showed that the most probable position for the hydrogen loss is the sp3 carbon in the five-membered ring. Calculations of the C13H9 harmonic vibrational frequencies are shown to match the experimental Raman (and infrared) bands well. A new electronic transition is identified at 283.1 nm (4.38 eV). Its position agrees with earlier time-dependent density functional theory calculations. Oscillator strengths for this transition and three others are estimated. The electronic transitions in the dehydrogenated species, C13H9, are strongly red-shifted compared to fluorene. The neutral open-shell species C13H9 formed from fluorene, C13H10, by low-energy electron bombardment and by ultraviolet photolysis in an argon matrix at 12 K has been studied via preresonance Raman, infrared, and ultraviolet/visible spectroscopy. Density functional theory calculations (B3LYP/6-31G(d,p)) of the CH bond energies of neutral fluorene showed that the most probable position for the hydrogen loss is the sp3 carbon in the five-membered ring. Calculations of the C13H9 harmonic vibrational frequencies are shown to match the experimental Raman (and infrared) bands well. A new electronic transition is identified at 283.1 nm (4.38 eV). Its position agrees with earlier time-dependent density functional theory calculations. Oscillator strengths for this transition and three others are estimated. The electronic transitions in the dehydrogenated species, C13H9, are strongly red-shifted compared to fluorene.

Source Name

J. Phys. Chem. A

Publication Date

2002

Volume

106

Issue

30

Page(s)

6935-6940

Document Type

Citation

Citation Type

Article