The malonaldehyde equilibrium geometry: A major structural shift due to the effects of electron correlation
- 1 May 1985
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 82 (9) , 4194-4198
- https://doi.org/10.1063/1.448861
Abstract
Complete theoretical optimizations of the equilibrium geometry of malonaldehyde have been carried out within the framework of the self-consistent-field (SCF) approximation. Both Huzinaga–Dunning double zeta plus polarization (DZ+P) and Pople 6–31G** basis sets have been used, resulting in very similar results. The predicted O ⋅ ⋅ ⋅ H hydrogen bond distance is 1.88 Å, in poor agreement with the value 1.68 Å deduced from experiment. It appears that the Hartree–Fock approximation is incapable of describing the equilibrium geometry of malonaldehyde in a qualitatively correct manner. However, second-order perturbation theory yields a structure (O ⋅ ⋅ ⋅ H distance 1.69 Å) in good agreement with experiment. The structures of the keto tautomer and the transition state for symmetric intramolecular hydrogen transfer have also been determined, as have harmonic vibrational frequencies for all stationary points.Keywords
This publication has 23 references indexed in Scilit:
- Microwave spectroscopic study of malonaldehyde. 4. Vibration-rotation interaction in parent speciesJournal of the American Chemical Society, 1984
- Microwave spectroscopic study of malonaldehyde. 3. Vibration-rotation interaction and one-dimensional model for proton tunnelingJournal of the American Chemical Society, 1984
- The infrared spectrum of gaseous malonaldehyde (3-hydroxy-2-propenal)Spectrochimica Acta Part A: Molecular Spectroscopy, 1983
- On the infrared spectrum of malonaldehyde, a tunneling hydrogen-bonded moleculeJournal of Molecular Spectroscopy, 1982
- Microwave spectroscopic study of malonaldehyde (3-hydroxy-2-propenal). 2. Structure, dipole moment, and tunnelingJournal of the American Chemical Society, 1981
- Ab initio molecular orbital studies of sigmatropic rearrangementsInternational Journal of Quantum Chemistry, 1978
- Correlation effects on barriers to proton transfer in intramolecular hydrogen bonds. The enol tautomer of malondialdehyde studied by ab initio SCF-CI calculationsJournal of the American Chemical Society, 1976
- The intramolecular hydrogen bond in malonaldehydeJournal of the American Chemical Society, 1976
- Molecular orbital studies of hydrogen bonds. VIII. Malonaldehyde and symmetric hydrogen bonding in neutral speciesJournal of the American Chemical Society, 1975
- Intramolecular hydrogen bond. Ab initio MO calculations on the enol tautomer of malondialdehydeJournal of the American Chemical Society, 1975