Fourier transform infrared matrix-isolation analysis of acetaldehyde fragmentation products after charge exchange with Ar•+ under varied ionization density conditions.

The products of the Ar(•+) charge exchange ionization of acetaldehyde have been isolated and compared with related photoionization results and computational work. Acetaldehyde has been used to assess the effect of varied ion density in the ionization region of the electron bombardment matrix isolation apparatus. The amount of acetaldehyde destruction has been measured for constant gas-sample composition and constant ionization current for two anode geometries: a pin anode and a plate anode. For the same ionization current, a pin-shaped anode demonstrates higher precursor molecule destruction efficiency (85%) than the plate-shaped anode (30%), resulting in substantial effect on the yield and quantity of isolated products. When the plate anode is used, the observed infrared products correspond to matrix-isolated carbon monoxide (CO), methane (CH(4)), ketene (CH(2)CO), ethynyloxy radical (HCCO), formyl radical (HCO(•)), acetyl radical (CH(3)CO(•)), vinyl alcohol (H(2)C = CH-OH), and cationic proton-bound dimer, Ar(2)H(+). When the pin anode is used, the same products are observed with different relative proportions and new absorption features corresponding to dicarbon monoxide (CCO) and methyl radical (CH(3)(•)) are observed. The surprising observation of infrared absorptions corresponding to vinyl alcohol along with low yield of products anticipated through the analysis of photoelectron-photoionization coincidence measurements suggests that the initially formed fragmentation products are able to further react within the matrix-isolation environment to influence observed product yields. Related experiments, using the isotopomer CD(3)CHO, suggest that the observed products are formed via radical-radical reactions that occur under the high pressure conditions of the matrix isolation environment.