Discrimination of rotamers of aryl alcohol homologues by infrared-ultraviolet double-resonance spectroscopy in a supersonic jet

Infrared-ultraviolet double-resonance spectroscopy has been applied to disc riminate rotamers of jet-cooled aryl alcohol homologues, phi-(CH2)(n)OH, wh ere phi represents phenyl group and n = 1, 2, and 3 correspond to benzyl, p henethyl, and 3-phenylpropyl alcohols, respectively. Experimental results i ndicate that different OH stretching frequencies are associated with differ ent rotamers and that the ability of intramolecular hydrogen bonding with t he benzene pi-electron decreases with an increase in alkyl chain length. In each aryl alcohol, the most prominent species in jets corresponds to the n on-hydrogen-bonded rotamer having higher OH stretching frequency.