The enthalpies of H-bond formation between 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as donor and tertiary amines of varying pK(a)'s as acceptors were determined by isothermal calorimetry. The stretching frequencies of the alphaC-D of HFIP-d(2) in dilute solution and in different H-bonded amine solvents were measured by Raman spectroscopy. Dilute HFIP-d(2) in chloroform showed two C-D stretching features at 2195 and 2168 cm(-1) which are assigned to the anti and gauche conformations of the molecule on the basis of precedent and theoretical calculations. The molecular structure, relative energies, and C-D stretching frequency (VC-D) Of the anti and gauche conformations of HFIP and HFIP-d(2) and their H-bonded complexes with trimethylamine were calculated by density functional theory using a B3LYP/6-31+G(d,p) basis set. In the monomeric state, the calculated VC-D for the gauche conformation was 52 cm(-1) lower than the anti conformations. Both VC-D bands were red-shifted when the O-H(D) group functioned as a H-bond donor with amine receptors. Among the different tertiary amines, the alcohol forms the weakest H bond with N,N-dimethylaniline and the strongest bond with quinuclidine. The enthalpy of H-bond formation and the gauche and anti aC-D, stretching frequencies were correlated, having slopes of -2 +/- 1 and -4 +/- 1.5 cm(-1)/(kcal mol(-1)), respectively. The results indicate increasing H-bond strength results in an increase in negative hyperconjugation of the vicinal C-D bond. Observation Of VC-D of specifically labeled (HO)C-D groups can be used to provide a spectroscopic characterization of a specific H bond present in macromolecular complexes when the OH group is bound to a single H-bond acceptor.