Current atmospheric models underestimate the production of organic acids in the troposphere. We report a detailed kinetic model of the photochemistry of acetaldehyde (ethanal) under tropospheric conditions. The rate constants are benchmarked to collision-free experiments, where extensive photo-isomerization is observed upon irradiation with actinic ultraviolet radiation (310 to 330 nanometers). The model quantitatively reproduces the experiments and shows unequivocally that keto-enol photo-tautomerization, forming vinyl alcohol (ethenol), is the crucial first step. When collisions at atmospheric pressure are included, the model quantitatively reproduces previously reported quantum yields for photodissociation at all pressures and wavelengths. The model also predicts that 21 ± 4% of the initially excited acetaldehyde forms stable vinyl alcohol, a known precursor to organic acid formation, which may help to account for the production of organic acids in the troposphere.

Measuring the isotopic abundance of hydrogen versus deuterium atoms is a key method for interrogating reaction pathways in chemistry. H/D 'scrambling' is the intramolecular rearrangement of labile isotopes of hydrogen atoms and when it occurs through unanticipated pathways can complicate the interpretation of such experiments. Here, we investigate H/D scrambling in acetaldehyde at the energetic threshold for breaking the formyl C-H bond and reveal an unexpected unimolecular mechanism. Laser photolysis experiments of CD₃CHO show that up to 17% of the products have undergone H/D exchange to give CD₂H + DCO. Transition-state theory calculations reveal that the dominant mechanism involves four sequential H- or D-shifts to form CD₂HCDO, which then undergoes conventional C-C bond cleavage. At the lowest energy the molecule undergoes an average of 20 H- or D-shifts before products are formed, evincing significant scrambling of H and D atoms. Analogous photochemically induced isomerizations and isotope scrambling are probably important in both atmospheric chemistry and combustion reactions.

The dynamics of CO production from photolysis of HCO have been explored over a 8000 cm energy range (345 nm-266 nm). Two-dimensional ion imaging, which simultaneously measures the speed and angular momentum distribution of a photofragment, was used to characterise the distribution of rotational and translational energy and to quantify the branching fraction of roaming, transition state (TS), and triple fragmentation (3F) pathways. The rotational distribution for the TS channel broadens significantly with increasing energy, while the distribution is relatively constant for the roaming channel. The branching fraction from roaming is also relatively constant at 20% of the observed CO. Above the 3F threshold, roaming decreases in favour of triple fragmentation. Combining the present data with our previous study on the H-atom branching fractions and published quantum yields for radical and molecular channels, absolute quantum yields were determined for all five dissociation channels for the entire S←S absorption band, covering almost 8000 cm of excitation energy. The S radical and TS molecular channels are the most important over this energy range. The absolute quantum yield of roaming is fairly constant ∼5% at all energies. The T radical channel is important (20%-40%) between 1500 and 4000 cm above the H + HCO threshold, but becomes unimportant at higher energy. Triple fragmentation increases rapidly above its threshold reaching a maximum of 5% of the total product yield at the highest energy.

We describe a new, simple theory for predicting the branching fraction of products in roaming reactions, compared to the analogous barrierless bond dissociation products. The theory uses a phase space theory (PST) formalism to divide reactive states in the bond dissociation channel into states with enough translational energy to dissociate and states that may roam. Two parameters are required, ΔEroam, the energy difference between the bond dissociation threshold and the roaming threshold, and the roaming probability, Proam, the probability that states that may roam do roam rather than recombine to form reactants. The PST-roaming theory is tested against experimental and theoretical data on the dissociation dynamics of H2CO, NO3, and CH3CHO. The theory accurately models the relative roaming to bond dissociation branching fraction over the experimental or theoretical energy range available in the literature for each species. For H2CO, fixing ΔEroam = 146 cm(-1), the midpoint of the experimental bounds for the roaming threshold, we obtain Proam = 1. The best-fit value, ΔEroam = 161 cm(-1), is also consistent with the experimental bounds. Using this value, the relative roaming to dissociation branching ratios are predicted to be similar in D2CO and H2CO, consistent with experimental observation. For NO3, we fix ΔEroam = 258.6 cm(-1), the experimental threshold for NO + O2 production, and we model low-temperature experimental branching fractions using the experimental rotational and vibrational temperatures of Trot = 0 K and Tvib = 300 K. The best fit to the experimental data is obtained for Proam = 0.0075, with this very small Proam being consistent with the known geometric constraints to formation of NO + O2. Using Proam = 0.0075, our PST-roaming theory also accurately predicts the low-temperature NO yield spectrum and quantum yield data for room-temperature NO3 photolysis. For CH3CHO, we fix ΔEroam = 385 cm(-1), based on theoretical calculations, and obtain a best-fit value of Proam = 0.21, fitting to reduced dimensional trajectory calculations. These values of ΔEroam and Proam yield PST-roaming theory results that are also consistent with two experimental room-temperature data points. The combination of other kinetic theories and the PST-roaming theory will provide rate coefficients for roaming reactions.

The photodissociation dynamics of H2CO molecules at energies bracketing the triple fragmentation threshold were investigated using velocity map ion imaging of the H-atom fragments. An algorithm was developed to model the experimental results as a two-step process: initially barrierless C-H bond fission on the S0 potential energy surface to form H + HCO, followed by secondary fragmentation of those HCO radicals with sufficient internal energy to overcome the small exit channel barrier on the HCO surface to form H + CO. Our model treats the first step using phase space theory (PST) and the second using a combined PST-impulsive model, with a tunneling correction. Experimentally, triple fragmentation reaches 25% of the radical (H + HCO) channel photochemical yield at energies about 1500 cm(-1) above the barrier for breaking the second bond. In addition, the triplet (T1) channel appears to reduce in importance after the barrier on the T1 surface is exceeded, slowly decreasing to <10% of the total radical yield at higher energy. The double PST-impulsive model provides a good fit to the experimental H-atom speed and energy distributions for H2CO dissociation on S0 spanning >7000 cm(-1) of available energy.