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 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.