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 language | English |
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Pages (from-to) | 2534-2538 |
Number of pages | 5 |
Journal | Physical Chemistry Chemical Physics |
Volume | 4 |
Issue number | 12 |
DOIs | |
Publication status | Published - 2002 |
Keywords
- HOLE-BURNING SPECTROSCOPY
- KINETIC-ENERGY SPECTROSCOPY
- METHYL-GROUP
- INTERNAL-ROTATION
- CATIONS
- THRESHOLD