Quantum states of hydrogen transfer and vibration in malonaldehyde

New ab initio results on the 21D potential energy surface of malonaldehyde and a quantum mechanical treatment of the hydrogen transfer motion and its interaction with all vibrations are presented. An explicit approximate reaction path, close to the minimum energy path but matching the reactive normal mode near equilibrium, allows one to predict the ground state tunnelling frequency even when using small basis sets. With a barrier of 1144 cm−1 (3.27kcal mol-1) the tunnelling splitting is predicted to be 22.0cm−1 for the parent species and 3.8 cm−1 for the species deuterated in the hydrogen bond, in good agreement with the observed values 21.6 and 2.9 cm−1, respectively. Predicted energy levels for excited states of the hydrogen transfer motion and for the non-reactive vibrations suggest a re-examination of the vibrational spectra and an extension of the number of vibrational factors in the basis set to improve the results for the vibrationally excited states.