Autoionization-detected infrared spectroscopy of intramolecular hydrogen bonds in aromatic cations. I. Principle and application to fluorophenol and methoxyphenol

Abstract

A new infrared spectroscopic technique for jet-cooled molecular cations is applied to observe intramolecular hydrogen bonds in substituted phenol ions. Vibrational transitions of an ion core of high Rydberg states are measured by detecting molecular ions prepared through vibrational autoionization. The observed infrared spectra practically provide vibrational frequencies of the corresponding bare molecular ion. The OH stretching vibrations of ortho-, meta-, and para-isomers of fluorophenol and methoxyphenol cations are observed. The OH stretching vibrational frequency of the ortho-isomer shows a characteristic redshift due to the intramolecular hydrogen bond. The redshift increases with ionization, indicating a significant enhancement of the intramolecular hydrogen bond strength.