Spectroscopic Studies of the Hydrogen Bond. II. The Shift of the O–H Vibrational Frequency in the Formation of the Hydrogen Bond

Abstract

The association spectra of a number of acids and alcohols in the region λλ9000–11,000 have been observed both in solution and in the pure liquids. In each case a broad band with maximum near λ10,000 was observed while in the alcohols an additional weaker band near λ9000 appears to be present. Evidence is presented that the λ10,000 band is to be identified with the O–H group. This evidence includes the behavior of the association band with change in concentration and temperature and its presence in several substances in which absorption other than that due to the O–H group is practically absent in the region studied. New evidence is given that a weak intermolecular hydrogen bond is formed between acetone and methyl alcohol. It is pointed out that the presence of absorption in the narrow O–H bands is not to be taken as evidence of the absence of hydrogen bonds in case the absorption is weak. The character of the O–H absorption in the case of intermolecular hydrogen bonds is discussed and the probable nature of the spectrum in the case of an intramolecular bond is indicated. A relation between the energy of the hydrogen bond and the shift of the O–H vibrational frequency is pointed out and its use is suggested in the interpretation of certain spectra.

Effects of structural variations on the hydrogen bond pairing between adenine derivatives and thymine

“…In accordance with the rule of Badger and Bauer [71] a linear dependence between the energy of hydrogen bonding and N 6 -H 6 stretching frequency in the hydrogen-bonded adenine-thymine complexes is established (correlation coefficient, r = 0.985). The shifts of N-H frequencies upon com-plexation are intrinsically related to interactions energies, in contrast to the respective values in the isolated monomers.…”

On the nature of halogen bonded complexes between carbonyl bases and chlorotrifluoromethane

“…For isolated CClF 3 the ν(C-Cl) stretching As demonstrated in numerous hydrogen-bonded systems, the interaction energies and the frequency shifts of the stretching vibration of the bond involved in the interaction are linearly related. This correlation was originally referred as the Badger-Bauer correlation [76,77].…”

Calculations on vibrational properties of H-bonded OH groups, as a function of H-bond geometry

“…(5 kcal mol-'). Thus, the Badger-Bauer rule [18], which proposes a linear relation between the enthalpy of a H bond and the shift in frequency of the OH bond, does not hold for different orientations of a given H-bonding systems (e.g., (H,O),).…”