jp5b10405_si_001.pdf (326.4 kB)

Download file# Self-Associating Behavior of Acetone in Liquid Krypton

journal contribution

posted on 2016-01-25, 00:00 authored by Liene I. De Beuckeleer, Wouter A. HerreboutAcetone
molecules are inclined to self-associate through dipole–dipole
interactions because of their large dipole moment. Infrared spectroscopy
of compounds dissolved in liquid noble gases supported by high level

*ab initio*calculations allows investigating the self-associating behavior and determining the thermodynamical properties. In this study, infrared spectra of various concentrations of acetone dissolved in liquid krypton are recorded at constant temperature. Overlapping monomer and dimer spectra are separated by analyzing the obtained data sets with numerical methods based on least-squares fitting. Although acetone is known to self-associate, only a few spectral features have been presented in literature before. In this study, the application of new numerical approaches succeeds in resolving overlapping spectra and allows observing isolated acetone dimer absorption bands for the complete mid infrared spectrum. By use of data sets of spectra recorded at temperatures between 134 and 142 K, the experimental standard dimerization enthalpy was determined to be −10.8 kJ mol^{–1}. MP2/aug-cc-pVDZ calculations predicted a stacked and planar dimer geometry of which the stacked geometry is more stable. Combining MP2 energies and single point corrections involving CCSD(T) calculations and complete basis set extrapolations based on the MP2/aug-cc-pVDZ equilibrium geometry lead to complexation energy of −28.4 kJ mol^{–1}for the stacked geometry and −15.1 kJ mol^{–1}for the planar geometry. The corresponding values for the complexation enthalpies in solution, obtained by combining these values with corrections for thermal and solvent influences are −13.7 and −5.8 kJ mol^{–1}.