Photodissociation of phenol at 248 nm was studied using multimass ion imaging techniques. Photofragment translational energy distribution of H atom elimination was measured. The results demonstrate that H atom elimination occurs on the πσ* excited state which has repulsive potential-energy functions with respect to the stretching of OH bond. It supports the recent ab initio calculation.

Photodissociation of nitrobenzene at 193, 248, and 266nm and o-nitrotoluene at 193 and 248nm was investigated separately using multimass ion imaging techniques. Fragments corresponding to NO and NO2 elimination from both nitrobenzene and o-nitrotoluene were observed. The translational energy distributions for the NO elimination channel show bimodal distributions, indicating two dissociation mechanisms involved in the dissociation process. The branching ratios between NO and NO2 elimination channels were determined to be NO∕NO2=0.32±0.12(193nm), 0.26±0.12(248nm), and 0.4±0.12(266nm) for nitrobenzene and 0.42±0.12(193nm) and 0.3±0.12(248nm) for o-nitrotoluene. Additional dissociation channels, O atom elimination from nitrobenzene, and OH elimination from o-nitrotoluene, were observed. New dissociation mechanisms were proposed, and the results are compared with potential energy surfaces obtained from ab initio calculations. Observed absorption bands of photodissociation are assigned by the assistance of the ab initio calculations for the relative energies of the triplet excited states and the vertical excitation energies of the singlet and triplet excited states of nitrobenzene and o-nitrotoluene. Finally, the dissociation rates and lifetimes of photodissociation of nitrobenzene and o-nitrotoluene were predicted and compared to experimental results.

In past studies, mistakes in determining the ionization mechanism in matrix-assisted laser desorption/ionization (MALDI) were made because an inappropriate ion-to-neutral ratio was used. The ion-to-neutral ratio of the analyte differs substantially from that of the matrix in MALDI. However, these ratios were not carefully distinguished in previous studies. We begin by describing the properties of ion-to-neutral ratios and reviews early experimental measurements. A discussion of the errors committed in previous theoretical studies and a comparison of recent experimental measurements follow. We then describe a thermal proton transfer model and demonstrate how the model appropriately describes ion-to-neutral ratios and the total ion intensity. Arguments raised to challenge thermal ionization are then discussed. We demonstrate how none of the arguments are valid before concluding that thermal proton transfer must play a crucial role in the ionization process of MALDI.

The dissociation rate of benzene and d6-benzene were measured under collision-free condition by multimass ion imaging techniques. The value of 1±0.2×105 s−1 and 5±1×104 s−1 were obtained for benzene and d6-benzene, respectively, with internal energy of 618 kJ/mol. The dissociation rate of benzene with internal energy of 483 kJ/mol was too slow to be measured, and the upper limit of the dissociation rate was estimated to be 3×103 s−1.

Collision-induced dissociation (CID) of sodiated glucose was investigated using electronic structure calculations and resonance excitation in a low-pressure linear ion trap. The major dissociation channels in addition to desodiation are dehydration and C₂H₄O₂ elimination reactions which the barrier heights are near to or lower than the sodiation energy of glucose. Dehydration reaction involves the transfer of the H atom from the O2 atom to the O1 atom, followed by the cleavage of the C1–O1 bond. Notably, α-glucose has a dehydration barrier lower than that of β-glucose. This difference results in the larger branching ratio of dehydration reactions involving α-glucose, which provides a simple and fast method for identifying the anomeric configurations of glucose. The C₂H₄O₂ elimination starts from the H atom transfer from the O1 atom to the O0 atom, followed by the cleavage of the C1–O0 bond. These results were further confirmed by experimental study using ¹⁸O-isotope-labeled compounds. Both the experimental data and theoretical calculations suggest that the dehydration reaction and cross-ring dissociation of sodiated carbohydrates mainly occur at the reducing end during low-energy CID.