Identification of individual conformers in C4H6O isomers using conformer-specific vibrational spectroscopy

We measured the conformer-specific vibrational spectra of C4H6O isomers in neutral and cationic states using IR resonant vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy for the first time. Notably, the measured IR dip and hole-burn VUV-MATI spectra for each isomer represent the identifiable vibrational spectra of individual conformers in both states. Furthermore, we estimated the relative populations of individual conformers in crotonaldehyde (CA) and methyl vinyl ketone (MVK) isomers using the IR dip intensity, the corresponding Franck–Condon factor, and the IR absorption cross section. Our analysis revealed that the compositional ratio of s-trans to s-cis conformers in the CA isomer remained at 95.8 : 4.2 even under supersonic expansion, whereas that in the MVK isomer was determined as 90.6 : 9.4, which is consistent with previous research. These findings reveal that the conformational stability of each isomer depends on the position of the methyl group relative to the carbonyl group.