Naslov
The intramolecular hydrogen bond in malonaldehyde as seen by infrared spectroscopy. A four-dimensional study

Autori
Došlić, Nađa ; Kuehn, Oliver

Izvornik
Zeitschrift fur Physikalische Chemie = International Journal of Research in Physical Chemistry & Chemical Physics (0942-9352) 217 (2003), 12; 1507-1524

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Intramolecular Hydrogen Bond; Malonaldehyde; Infrared Spectroscopy

Sažetak
The infrared spectrum of the O--H--O fragment of malonaldehyde is studied using a four-dimensional model. This comprises the OH stretching, the two OH bendings as well an O-O ring deformation mode under the assumption of overall C$_{; ; ; \rm s}; ; ; $ symmetry. The full anharmonic potent ial energy and dipole moment surfaces are calculated using density functional theory and the re spective vibrational eigenvalue problem is solved by an iterative Lanczos method. Fundame ntal and combination transitions are discussed for the normal species and the symmetrical ly deuterated isotopomer. Special emphasis is paid to the OH/OD stretching region which reveal s the signatures of strong mode mixing what renders a simple assignment in terms of fundamental tran sitions difficult. In addition results for hot transitions are presented which show a rather differ ent OH/OD band due to the topology of the potential energy surface. The influence of H atom tunneli ng on the spectrum is briefly addressed.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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