The Intramolecular Hydrogen-Bond in Malonaldehyde as Seen by Infrared Spectroscopy. A Four-Dimensional Model Study

Abstract

Abstract The infrared spectrum of the O–H–O fragment of malonaldehyde is studied using a four-dimensional model. This comprises the OH stretching and the two OH bending vibrations as well an O–O ring deformation mode under the assumption of overall Cs symmetry. The full anharmonic potential energy and dipole moment surfaces are calculated using density functional theory and the respective vibrational eigenvalue problem is solved by an iterative Lanczos method. Fundamental and combination transitions are discussed for the normal species and the symmetrically deuterated isotopomer. Special emphasis is paid to the OH/OD stretching region which reveals the signatures of strong mode mixing what renders a simple assignment in terms of fundamental transitions difficult. In addition results for hot transitions are presented which show a rather different OH/OD band due to the topology of the potential energy surface. The influence of H atom tunneling on the spectrum is briefly addressed employing an alternative three-dimensional model which takes into account the in-plane H atom motion as well as the O–O distance.