Vibrational dynamics of carboxylic acid dimers in gas and dilute solution

Abstract

Ultrafast mid-IR transient absorption spectroscopy has been used to study the vibrational dynamics of hydrogen-bonded cyclic dimers of trifluoroacetic acid and formic acid in both the gas and solution phases (0.05 M in CCl₄). Ultrafast excitation of the broad O–H cyclic dimer band leads, in the gas phase, to large-scale structural changes of the dimer creating a species with a distinct free O–H stretching band on 20 ps and 200 ps timescales. These timescales are assigned to ring-opening and dissociation of the dimer, respectively. In the solution phase, no such structural rearrangement occurs and our results are consistent with previous studies. The gas phase dynamics are insensitive to both the specific excitation energy (over a span of 550 cm⁻¹) and the chemical identity of the dimer.