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Fast nonradiative decay in o-aminophenol.

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  • 1Instituto de Investigaciones en Físico Química de Córdoba (INFIQC) CONICET, UNC. Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Ciudad Universitaria , X5000HUA Córdoba, Argentina.

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Summary

The gas phase structure of 2-aminophenol was studied using spectroscopy. Its trans isomer exhibits a very short excited state lifetime due to strong electronic state coupling.

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Area of Science:

  • Molecular Spectroscopy
  • Physical Chemistry
  • Quantum Chemistry

Background:

  • 2-aminophenol is a molecule with potential for intramolecular hydrogen bonding.
  • Understanding its gas phase structure and excited state dynamics is crucial for its chemical applications.

Purpose of the Study:

  • To determine the gas phase structure of 2-aminophenol.
  • To investigate the excited state lifetimes and electronic properties of its isomers.
  • To elucidate the factors contributing to its unique photophysical behavior.

Main Methods:

  • UV-UV and IR-UV hole burning spectroscopy were employed to study the gas phase structure.
  • Picosecond pump-probe experiments measured excited state lifetimes.
  • Ab initio calculations provided insights into electronic states and vibrational modes.

Main Results:

  • The cis isomer of 2-aminophenol was ruled out due to the absence of intramolecular hydrogen bonding.
  • The trans isomer showed a significantly short excited state lifetime of (35 ± 5) ps.
  • Franck-Condon simulations supported the experimental findings for the trans isomer.

Conclusions:

  • The gas phase structure is predominantly the trans isomer.
  • The short excited state lifetime is attributed to strong coupling between the first two singlet excited states.
  • The nonplanar geometry of the trans isomer in the excited state contributes to this coupling.