Abstract
Abstract Anharmonic IR spectra of H-bonded and non-H-bonded conformers of malonaldehyde (MA) and its isotopomers MA-D 6 D 8 and MA-D 7 D 9 have been computed by the Vibrational-Self-Consistent-Field (VSCF) and the correlation-corrected-VSCF (CC-VSCF) techniques using ab initio MP2/6-31G*(+p) potential energies. The agreement between the experimental and calculated frequencies is significantly improved to within 2–3%. Anharmonic contributions are substantial especially for ν OH of the H-bonded form, by reducing the harmonic value by more than 500 cm −1 . The effect is less important in the non-H-bonded form. The ν OH stretching mode is strongly coupled with the ν 3 mode (essentially ν CH 7 ) and with the in-plane and out-of-plane OH bending deformations. H-bond formation and deuteration batochromically shift ν OH by an amount which is influenced by the anharmonic terms, the major contribution arising from coupling between modes. The comparison with the ν OH mode of some other H-bonded systems suggests that anharmonic correction follows H-bonding strength.
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