Communication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer

The highest frequency hydrogen bond fundamental of formic acid dimer, ν 24 (B u ), is experimentally located at 264 cm −1 . FTIR spectra of this in-plane bending mode of (HCOOH) 2 and band centers of its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presente...

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Bibliographic Details
Published in:The Journal of chemical physics 2012-04, Vol.136 (15), p.151101-151101-4
Main Authors: Kollipost, F., Larsen, R. Wugt, Domanskaya, A. V., Nörenberg, M., Suhm, M. A.
Format: Article
Language:English
Subjects:
Dimers
Dissociation energy
Formic acid
Free energy
Heat of formation
Hydrogen bonds
Slits
Spectra
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Summary:The highest frequency hydrogen bond fundamental of formic acid dimer, ν 24 (B u ), is experimentally located at 264 cm −1 . FTIR spectra of this in-plane bending mode of (HCOOH) 2 and band centers of its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presented. Comparison to earlier studies at room temperature reveals the large influence of thermal excitation on the band maximum. Together with three B u combination states involving hydrogen bond fundamentals and with recent progress for the Raman-active modes, this brings into reach an accurate statistical thermodynamics treatment of the dimerization process up to room temperature. We obtain D 0 = 59.5(5) kJ/mol as the best experimental estimate for the dimer dissociation energy at 0 K. Further improvements have to wait for a more consistent determination of the room temperature equilibrium constant.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4704827