The PFI-ZEKE photoelectron spectrum of m-fluorophenol and its aqueous complexes: Comparing intermolecular vibrations in rotational isomers

K Yosida, K Suzuki, S Ishiuchi, M Sakai, M Fujii, C E H Dessent, K Muller-Dethlefs

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Abstract

Pulsed field ionization zero kinetic energy (PFI-ZEKE) photoelectron spectroscopy has been applied to study the cationic ground states of the rotational isomers of m-fluorophenol and its hydrogen-bonded clusters with H2O and D2O. The cis- and trans- monomer isomers are assigned by comparing the observed ionization potentials with values obtained from ab initio calculations (HF/6-31G*). Both monomers display very similar vibrational frequencies, indicating that the geometric structures of the two cations are similar. In contrast, the cis- and trans- aqueous clusters display distinctive intermolecular vibrational frequencies (e.g. the intermolecular stretching vibrations appear at 239 and 228 cm(-1) in the cis- and trans- isomers respectively). The origin of the different intermolecular interactions in the isomeric clusters is discussed with reference to the ab initio calculations.

Original languageEnglish
Pages (from-to)2534-2538
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume4
Issue number12
DOIs
Publication statusPublished - 2002

Keywords

  • HOLE-BURNING SPECTROSCOPY
  • KINETIC-ENERGY SPECTROSCOPY
  • METHYL-GROUP
  • INTERNAL-ROTATION
  • CATIONS
  • THRESHOLD

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