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Hyperthermal collisions of ground-state atomic oxygen with H2O have been investigated, with special attention paid to the H-atom elimination reaction, O(3P) H2O(X 1A1) → HO2(2A‘) H(2S). This reaction was observed in a crossed-beams experiment, and the relative excitation function in the region around its energy threshold (50−80 kcal mol-1) was measured. Direct dynamics calculations were also performed at two levels of theory, B3LYP/6-31G(d,p) and MP2/6-31G(d,p). The shape of the B3LYP excitation function closely matches that of the experiment. The calculations provided a detailed description of the dynamics and revealed a striking dependence of the reaction mechanism on collision energy, where the cross section rises from a threshold near 60 kcal mol-1to a peak at ∼115 kcal mol-1and then decreases at higher energies as secondary dissociation of the internally excited HO2product becomes dominant. The calculations show that the cross section for H-atom elimination (O H2O → HO2H) is about 10−25% that of the H-atom abstraction (O H2O → OH OH) cross section for collision energies in the 70−160 kcal mol-1range. [ABSTRACT FROM AUTHOR]

The unimolecular fragmentation of metastable anisole dications is studied by tandem-mass spectrometry. Permutations of OH, OCH3, and NH2 substituents as well as extensive labeling experiments are used as probes to unravel the mechanisms of the various fragmentation pathways observed. The main channel corresponds to methyl ion elimination, which leads to an energetically favorable charge separation (“Coulomb explosion”). Loss of a neutral CO molecule forms another important branch, and the expelled CO has incorporated a carbon atom from the phenyl ring of anisole. Substitution of the anisole dication with OH, OCH3, and NH2 groups results in more specific fragmentations. Ortho- and para-substitutions lead to preferential methyl ion elimination, whereas meta-substitution favors CO loss. The substituent effects are also reflected in pronounced changes in the apparent kinetic isotope effects upon substitution of OCH3 by OCD3. On the basis of the various experimental findings and some explorative DFT calculations, possible mechanisms for the skeletal rearrangements prior to CO elimination are proposed. [ABSTRACT FROM AUTHOR]

A direct ab initio dynamics study is carried out for three channels of the unimolecular reaction of fluoromethoxy, CH2FO. The minimum energy paths (MEPs) of the three channels are computed with the MPW1K/6-31+G(d,p) method. The geometries, harmonic vibrational frequencies, energies, and enthalpies of all stationary points are calculated at the MPW1K and QCISD levels of theory in conjunction with the 6-31+G(d,p) basis set. The energies of stationary points and the points along MEP for each channel are further refined by using single-point multilevel energy calculations. The rate constants are evaluated by means of the conventional transition state theory (TST), the canonical varitional transition state theory (CVT), and the canonical varitional transition state theory with small-curvature tunneling correction (CVT/SCT) in the temperature range of 200-2500 K. The fitted Arrhenius expressions of the calculated CVT/SCT rate constants are k1CVT/SCT(T) = (1.26 × 106)T2.19e-7150.6/T s-1, k2CVT/SCT(T) = (3.68 × 102)T3.23e-12327.7/T s-1, k3CVT/SCT(T) = (9.97 × 10-26)T10.90e-3873.3/T s-1 for the H elimination, HF elimination, and isomerization channels, respectively. [ABSTRACT FROM AUTHOR]