Measuring acetic acid dimer modes by ultrafast time-domain Raman spectroscopy

作者:Heisler Ismael A*; Mazur Kamila; Yamaguchi Sayuri; Tominaga Keisuke; Meech Stephen R
来源:Physical Chemistry Chemical Physics, 2011, 13(34): 15573-15579.
DOI:10.1039/c1cp20990f

摘要

Acetic acid is capable of forming strong multiple hydrogen bonds and therefore different dimeric H-bonded structures in neat liquid phase and in solutions. The low frequency Raman spectra of acetic acid (neat, in aqueous solution and as a function of temperature) were obtained by ultrafast time and polarization resolved optical Kerr effect (OKE) measurements. Isotropic OKE measurements clearly reveal a specific totally symmetric mode related to the dimeric structure H-bond stretching mode. The effects of isotope substitution, water dilution and temperature on this mode were investigated. These results together with anisotropic OKE measurements and density functional theory calculations for a number of possible dimers provide strong evidence for the cyclic dimer structure being the main structure in liquid phase persisting down to acetic acid concentrations of 10 M. Some information about the dimer structure and concentration dependence was inferred.

  • 出版日期2011