Communication: photodissociation of CH3CHO at 308 nm: observation of H-roaming, CH3-roaming, and transition state pathways together along the ground state surface.

Following photodissociation of acetaldehyde (CH3CHO) at 308 nm, the CO(v = 1-4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH3CO core and CH3-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem.

Photodissociation of CH3CHO at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: verification of roaming and triple fragmentation.

By using time-resolved Fourier-transform infrared emission spectroscopy, the HCO fragment dissociated from acetaldehyde (CH3CHO) at 248 nm is found to partially decompose to H and CO. The fragment yields are enhanced by the Ar addition that facilitates the collision-induced internal conversion. The channels to CH2CO + H2 and CH3CO + H are not detected significantly.

Photodissociation of Propionaldehyde at 248 nm: Roaming Pathway as an Increasingly Important Role in Large Aliphatic Aldehydes.

Time-resolved Fourier transform infrared emission spectroscopy is employed in the photolysis of propionaldehyde (CH3CH2CHO) at 248 nm to characterize the role of the roaming pathway. High-resolution spectra of CO are analyzed to yield a single Boltzmann rotational distribution for each vibrational level (ν = 1-4) with small rotational and large vibrational energy disposals. A roaming saddle point is found containing two far separated moieties of HCO and CH3CH2 with a weak interaction between them.

Association structures of ionic liquid∕DMSO mixtures studied by high-pressure infrared spectroscopy.

Using high-pressure infrared methods, we have investigated close interactions of charge-enhanced C-H-O type in ionic liquid∕dimethyl sulfoxide (DMSO) mixtures. The solvation and association of the 1-butyl-3-methylimidazolium tetrafluoroborate (BMI(+)BF(4)(-)) and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMM(+)BF(4)(-)) in DMSO-d(6) were examined by analysis of C-H spectral features. Based on our concentration-dependent results, the imidazolium C-H groups are more sensitive sites for C-H-O than the alkyl C-H groups and the dominant imidazolium C-H species in dilute ionic liquid∕DMSO-d(6) should be assigned to the isolated (or dissociated) structures.