caa a22 4500 378862774 CHVBK 20180305123350.0 cr unu---uuuuu 161128e20031201xx s 000 0 eng 10.1524/zpch.217.12.1507.20477 doi (NATIONALLICENCE)gruyter-10.1524/zpch.217.12.1507.20477 The Intramolecular Hydrogen-Bond in Malonaldehyde as Seen by Infrared Spectroscopy. A Four-Dimensional Model Study [Elektronische Daten] [Nadja Došlić, O. Kühn] 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. © 2003 Oldenbourg Wissenschaftsverlag GmbH Thermodynamics & statistical physics nationallicence Laboratory techniques, experiments nationallicence Physical chemistry nationallicence Došlić Nadja aut Kühn O. aut Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 217/12/2003(2003-12-01), 1507-1524 0044-3336 217:12/2003<1507 2003 217 zpch https://doi.org/10.1524/zpch.217.12.1507.20477 text/html Onlinezugriff via DOI 1 research article jats NATIONALLICENCE 856 40 https://doi.org/10.1524/zpch.217.12.1507.20477 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Došlić Nadja aut NATIONALLICENCE 700 1- Kühn O. aut NATIONALLICENCE 773 0- Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 217/12/2003(2003-12-01), 1507-1524 0044-3336 217:12/2003<1507 2003 217 zpch CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-gruyter