Vibrational overtone spectra of o-fluorophenol and the "anomalous" order of intramolecular hydrogen bonding strengths.

The near infrared vibrational overtone absorption spectrum of liquid phase o-fluorophenol is examined in the region deltav=2, 3 and 4. The OH frequencies are compared with that of o-chlorophenol and phenol. Considering the relative electronegativities of all halogens, one might expect the order of intramolecular hydrogen bond strength for o-fluorophenol to be the greatest among all halogenophenols. It is evident that o-fluorophenol forms a weaker intramolecular hydrogen bond (an anomalous trend) contrary to that expected from relative electronegativities of halogens. The local mode mechanical frequency values and anharmonicity values obtained from fitting the overtones are analysed. Our observation is in agreement with the previous experimental as well as the recent theoretical vibrational analysis of halogenophenols using density functional theory (B3LYP). The overtone spectra of o-fluorophenol in carbon tetrachloride in different concentrations are also examined. It is noted that the OH-red shift which arises due to the intermolecular bond formation between the cis and trans conformers of o-fluorophenol (dimerization) increases with concentration.