Formic acid-methanol complexation vs. esterification: elusive pre-reactive species identified by vibrational spectroscopy.

Vibrational spectra of the mixed dimer and the two mixed trimers of methanol and formic acid as well as some of their isotopologues are presented. Out of the eight expected OH stretching fundamentals of these three pre-reactive hydrogen-bonded complexes, the three modes mainly involving an acid OH group bound to the alcohol appear to be missing in the jet-cooled spectra despite a combination of infrared and Raman probing. A possibility of spectral overlap is discussed in the mixed dimer case, but largely discarded. The missing modes correspond to (fractional) concerted elongation of all engaged OH bonds, promoting synchronous degenerate proton transfer between the molecules. One other trimer mode is very tentatively attributed to a broad spectral feature, whereas all OH bonds contacting carbonyl groups can be unambiguously identified by four relatively narrow infrared absorptions. The spectral features are confirmed by vibrational perturbation theory and deviate in a subtle but systematic way from scaled harmonic predictions which were previously validated for the formic acid complex with a more acidic alcohol. Despite being exothermic and exergonic, ester formation can only be detected in the rarefied gas expansions after extended pre-mixture of the gases, which somewhat contrasts the recent microwave spectroscopic evidence of in situ ester formation and in particular the lack of pre-reactive complex signals.